Black Star defeats Mifune in their first match.
Black Star first appears with Tsubaki on a mission to take down Alcapone and his men. Although Tsubaki reminds him of the Way of Assassination, Black Star ends up giving himself away by making a big entrance right in the middle of the villains' banquet, using Tsubaki in Weapon form like a microphone, much to the Weapon's chagrin. Alcapone's men do not hesitate to attack them, and the two are forced to retreat using Tsubaki's Smoke bomb Mode.
Tsubaki is saddened by their failure, saying that they had not been able to acquire a single soul as of yet, but Black Star remains ecstatic, claiming that he was as 'big as usual' and made a great stage performance. The two contact Shinigami and Tsubaki tells them of their failed mission. Shinigami wonders on why they are failing so much even when they are quite skilled. Black Star interrupts and promises to turn Tsubaki into a Death Scythe, and offers him his autograph as a current substitute, which earns him a chop to the head by Shinigami.
Shinigami then tells them that although he would like to watch over them all the time, things have become problematic recently because Alcapone and his men have begun to go after a Witch Soul of the Witch Angela Leon. He also tells them that Angela has an incredibly strong bodyguard called Mifune and that his soul is more powerful than the average human's. His soul alone will count as ninety-nine souls. Realizing that Mifune's soul and Angela's Witch Soul would immediately turn Tsubaki into a Death Scythe, Black Star eagerly dashes off to face Mifune, with Tsubaki following behind, not waiting to listen to the rest of what Shinigami has to say about Angela.
Tsubaki however, stops Black Star and tells him that in their current state, it would be impossible to defeat Mifune and Angela. They would need to go through this mission properly. Angered by her criticism, Black Star attempts to prove to Tsubaki that he can easily follow the Way of Assassination, by sneaking up on Tsubaki whilst she is bathing at a waterfall. He manages to do it at first, but then ends up screaming when he sees her naked body, which causes an angry Tsubaki to throw a shuriken at him.
As the two make their way to Magic Castle Cinder where Angela and Mifune reside, Tsubaki asks Black Star if he has a plan. He confidently replies that the first thing he will do is make a big entrance, much to Tsubaki's despair. However, Black Star then swears to Tsubaki that he will make her into a Death Scythe, and she smiles and says that she knows he will.
However, as they reach the castle, they see Alcapone's men killed, and they are attacked by Mifune. Mifune asks them if they are after Angela. Black Star introduces himself to Mifune and declares a duel with him as he thinks he is quite strong. Mifune gives the two a chance to leave, but Black Star orders Tsubaki to change into Chain Scythe Mode. Noticing that Black Star is a person from Shibusen, Mifune prepares to attack, engaging in his Infinite One-Sword Style.
Mifune quickly proves to be more than a match for Black Star, as the Meister struggles against his swordsmanship. Mifune says so to Black Star, that his Weapon is the only thing protecting him, and that no matter how potent a Weapon is, if its Meister is not competent, it will be useless. He gives one last chance for Black Star to leave, saying that he does not like to kill a child. However, Black Star, angered at Mifune for calling him a child, proceeds to attack Mifune by throwing Tsubaki at him in Shuriken Mode, followed by Smoke bomb Mode, and then attempts to cut Mifune under cover of the smoke by grabbing one of his katanas. However, his loud voice gives him away, and Mifune strikes him down.
Tsubaki watches on, horrified, thinking Black Star is dead. However, the Meister gets up, and yells at Mifune for hitting him with the back of his blade, saying that only he can do those kind of moves. Mifune instead says he feels sorry for Tsubaki, as she has to put up with him. He calls Black Star a 'small kid.' However, Tsubaki defends Black Star, saying that he can succeed if he tries, despite being a bit of an idiot at times. Black Star, now furious at Mifune, accuses him for trying to stand out more than him, and declares that the main role will always be himself. Deciding to take the fight seriously, he successfully follows the Way of Assassination. By covering himself with Tsubaki's Smoke Bomb Mode, he uses Tsubaki's Dummy Star Mode to distract Mifune, before taking down Mifune with one hit using his Certain Kill: Black☆Star Big Wave. As Mifune is defeated, Black Star states that it obvious he lost to someone as great as him.
He proceeds to interrogate Mifune on the whereabouts of Angela. Mifune refuses to say anything and Black Star is about to lose his patience when Angela herself arrives and begs the two to spare Mifune. Black Star is startled as Angela is only a small child, and that Mifune is defending her until she can fend for herself. Mifune tells Black Star that he can take his soul, but he would fight to the death for Angela. In the end, Black Star does not kill the two, repeating Mifune's words as he leaves, that he would not like to kill a child.
Back at the DWMA, Black Star gives all of Alcapone and his mens' souls to Shinigami, who asks him why he is not taking them when the going is good. Black Star declares that someone as great as him has no need to take credit for someone else's work. He asks for Tsubaki's opinion and she happily agrees.
Later however, Black Star is back to his old tricks again, peeping on Tsubaki in the school baths, which earns him a shuriken thrown into his head.
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