The invention relates to the technical field of petroleum and natural gas drilling coring, in particular to a semiconductor refrigeration composite inner barrel for coring of combustible ice. A battery pack and a coordinated control system (CCS) are installed inside a protection joint of the semiconductor refrigeration composite inner barrel and are connected. An outer protection barrel and an inner protection barrel are connected to the lower end of the protection joint. The lower end of the outer protection barrel and the lower end of the inner protection barrel are both connected with the upper end of a lower protection joint. The outer protection barrel is arranged outside the inner protection barrel. A semiconductor flexible refrigeration belt is arranged between the outer protection barrel and the inner protection barrel. The CCS is connected with the semiconductor flexible refrigeration belt through a connection line. The semiconductor refrigeration composite inner barrel achieves the automatic control and refrigeration functions, and can automatically detect the temperature of a rock core of the inner barrel and then start a semiconductor refrigeration device according to the temperature, thereby achieving continuous refrigeration on the rock core of the inner barrel, preventing combustible ice from volatilizing due to time rising in the drilling process, and increasing the acquisition probability of combustible ice substances.