As space exploration activities and strategic deployments in polar regions continue to advance, higher demands have been placed on the low-temperature resistance of propellant binders. Here, high cis-1,4 content hydroxyl-terminated polybutadiene (HTPB) was successfully synthesized via an oxidative cleavage method using commercial cis-polybutadiene (BR). The microstructure, molecular weight, hydroxyl value, rheological behavior, thermal properties, and mechanical performance of the resulting cis-HTPB were systematically characterized. By adjusting the molar ratio of mCPBA to butadiene units, three cis-HTPB samples with varying molecular weights were obtained. The high cis-1,4 structure (93%) was preserved after modification. The synthesized cis-HTPB exhibited an ultra-low glass transition temperature (Tg) of approximately −100 °C and lower viscosity compared to commercial HTPB, indicating excellent low-temperature flexibility and processability. In addition, the cis-HTPB was further modified with acrylate groups to produce a UV-curable derivative (AcTPB). The cured AcTPB also retained a Tg near −100 °C, demonstrating its suitability for ultra-low-temperature applications and its promise as a photocurable binder for 3D printing propellant.