Hijikata was a samurai in Tosa Domain (modern-day Kōchi Prefecture). He was sent by the domain to Edo for studies, where he became involved in the "sonnō jōi" movement, and after returning to Tosa, he joined Takechi Hanpeita's movement. He travelled with Takechi to Kyoto in 1863, where he joined forces with the anti-Tokugawa shogunate forces of Chōshū Domain and made contact with the "kuge" aristocracy, most notably Sanjō Sanetomi. After the abortive coup against the Shogunate later that year, he was forced into exile with Sanjō to Chōshū. Following the First Chōshū expedition, he fled to Fukuoka Domain together with Sanjō, where he later met with fellow Tosa countrymen Nakaoka Shintarō, and Sakamoto Ryōma whom he assisted in securing Sanjō’s support for the Satchō Alliance.