In this study, (B2O3)-B-10/polyimide (PI) hybrid materials were synthesized with the aim to improve their thermal stability and neutron shielding properties. 3,3'-Diaminodiphenyl sulfone (DADPS) reacted with 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) in N-methyl-2-pyrrolidone (NMP) and mixed with amine functionalized (B2O3)-B-10 to prepare a series of poly (amic acid), meanwhile, corresponding PIs were obtained via the thermal imidization procedures. The morphologies and structures of the prepared hybrid materials were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). The thermooxidative and flame retardancy properties of the PI films were examined by thermogravimetric analysis (TGA) and limiting oxygen A +/- ndex (LOI). The experimental results showed that as the amount of functionalized (B2O3)-B-10 was increased, flame retardant properties of the hybrid films were increased. Hybrid materials were also irradiated with thermal neutrons. The neutron shielding properties increasing depends on the amount and the distribution of the B-10 isotope.