Abstract With the development of new energy sources, the demand for aluminum composite films for power batteries is expanding; at the same time, higher requirements have been put forward for aluminum composite films and adhesives. Polyurethane, as the binder of aluminum composite films, strongly affects the performance of aluminum composite films when exposed to moisture and high temperature and can lead to delamination. This thesis prepares a polyurethane and silicone block copolymer composite adhesive by adjusting the ratio of hard and soft polyurethane segments to obtain polyurethane (PU) with excellent flexibility. On the basis of block copolymerization with bis‐amino‐terminated organosiloxane (ATPS), obtained excellent flexibility, high peel strength, moisture resistance, and heat resistance from a polysiloxane‐based polyurethane composite adhesive (PUSR). The properties are also tested using tensile tests and peel strength tests. The test results show that by adjusting the ATPS content, the flexibility and hydrophobicity of the PUSR composite adhesive further improved, with a tensile strength of 36 MPa, an elongation at break of 757%, and bonding performance of 11 N/15 mm. Additionally, the damp heat resistance of 6 N/15 mm, exceeding the international standard of 3 N/15 mm, in the power battery soft package aluminum–plastic film has potential application prospects.