Abstract: XPS was used to measure the shifts of N1s and O1s binding energies in the amide group of nylon11 combined with BiI₃ nanoparticles. Besides, attenuated total reflection infrared spectroscopy was used to study the complex effect of BiI₃ on hydrogen bonding in polyamide. Compared with nylon11, higher binding energies of N1s and O1s in BiI₃-nylon11 nanocomposites were observed. Before X-ray exposure, the N-H stretch frequency, amide I mode, and amide II mode in the vibrational spectra of BiI₃-nylon11 nanocomposits shifts remarkably relative to those of pure nylon11; however, the amide I and II mode in the vibrational spectra of composits are similar to those of nylon11 after X-ray irradiation, except that bands are broader. CH₂ stretching vibrations are, at large unaffected by the complexation whether or not being exposed to X-rays. These results are meaningful for the understanding of the hydrogen bonding in polymers and its effects on structure and properties.