A comparative study of properties of the films based on polyimide powders synthesized by chemical or thermal imidization is presented. It is shown that the imidization method affects the shape, size, bulk density, and size distribution of the synthesized polyimide powder particles, which influences the properties of the films obtained. The method of chemical modification allows to obtain denser powders comparing to the thermally imidized powder. The films were obtained with the help of selective laser sintering (SLS) for the first time. It is shown that the films produced by SLS from chemically imidized polyimide powder are more dense and monolithic as compared to those made from thermally imidized polyimide, which provides, obviously, higher mechanical characteristics of the former. They have the strength higher in 2.5 times and the elastic modulus twice as high than latter one. The optimal laser power is 65 W.