27 years old. Vice-Commander of the Shinsengumi. Feared within the corps as the "Demon Vice-Commander" and the "Brains of the Shinsengumi." He is the most popular man in the Shinsengumi and has handsome features, though his pupils are always somewhat dilated. He is exceptionally proud, serious, and cool-headed. He is relatively sensible and acts as the straight man (tsukommi). Although he has a blunt and stubborn attitude, he is caring and shows a clumsy kind of kindness. Since he deals with problem children both above and below him, he is good at providing support. Unusually for a serious character, he is blunt and rarely uses honorifics even with superiors, though he does use them with Shigeshige Tokugawa and students on field trips. He is a heavy smoker to the point that he becomes extremely emotionally unstable and turns into a dangerous person when deprived of cigarettes. An extreme mayonnaise addict (mayora), he not only believes there is nothing more delicious but thinks it should be poured on everything. He has a bad habit of forcing his tastes on others. Born as the illegitimate child of the prestigious Hijikata family in Bushu, his existence was discovered after the death of his playboy father. He was taken in by the Hijikata family after his mother's death. When he was 11, his village was hit by a great fire. Later, during his days as a "Baragaki" (thorny brat) causing trouble, he met Kondo and became a junior disciple in the same dojo. He excels at psychological warfare and strategy. By utilizing the terrain, he can hold his own and fight on equal terms even against enemies with superior raw strength. His quick thinking earned him the title of "Tactician" from Gintoki and is recognized by Kyuubei and Sasaki. Especially compared to Gintoki, while he may be inferior in physical strength, he seems to win in intelligence in a back-and-forth struggle. He has been loathed by Sougo Okita—his junior disciple from the Bushu days (about 10 years younger)—since they first met, due to Sougo's relationship with his sister Mitsuba and Kondo. Even as adults, Sougo is constantly aiming for his life. That relationship hasn't changed since Mitsuba's death, but in reality, they trust and care for each other; they are important to one another after all. Yamazaki says he is naive when it comes to women, but he denies this with all his might. He is dense regarding affection from others. Generally, he is a gentleman toward women. At the same time, he has a soft spot for them; when facing Yagyu Kyuubei, he hesitated to attack once he realized she was a woman. He harbored romantic feelings for Mitsuba Okita, but due to his upbringing, he believed that a man living in a world of blood could not make her happy. When she confessed her feelings to him back in Bushu, he deliberately pushed her away with cold words. The fact that her brother Sougo acknowledges how much Hijikata cherished Mitsuba speaks to the depth of his feelings for her. He refers to her as "the woman I fell for." When Mitsuba was facing her final moments on her sickbed, he did not attend. Mitsuba passed away a few months ago. She used to call him Toshiro-san. He loves Mitsuba.

Captain of the Shinsengumi First Division. A massive sadist. Sadistic. Speaks with an Edo dialect. One of the Shinsengumi's finest swordsmen. Deeply admires Isao Kondo and constantly aims for Toshiro Hijikata's life, both as a joke and in earnest. Mitsuba used to call him Sou-chan.

28 years old. Commander of the Shinsengumi. A stalker of Tae Shimura. A leader with great charisma who is deeply trusted by his men. Deeply admired by Hijikata and Okita. Often treated like a gorilla.

32 years old. Shinsengumi spy (Inspector). Plain. Does not wear glasses. With his plain looks and timid personality, he is teased by Hijikata and Okita, making him one of the most unfortunate characters in the series.