In this paper，PANI/SSA thin films were deposited by MAPLE technique with different lasers. The structures and composition of films were characterized by XPS. The XPS results showed that because of the protection of matrix, the main structures and composition of films were protected effectively during deposition. While different lasers bring different influence to film structures. To short-wave laser, photochemical effect is obvious, the structures related to doping showed obvious change. To long-wave laser, photochemical effect did not bring obvious change to related structures, the XPS peaks showed no difference to that of PANI/SSA powder.