Polymer materials are a class of materials of great importance for their peculiar chemical-physical properties. The basic principles of X-ray absorption fine structure (XAFS) which is promoted by synchrotron radiation, including extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) were introduced. Various XAFS methods were reviewed for applications in studies of polymers and related materials, including usual polymers, organometallic polymers, Pd-droped polymers, ionomers, carbon based materials, etc. These mentioned applications have showed the significance and advantage of XAFS in polymers and related materials field. It is confident that the promotion and growth in XAFS would bring more benefits in scientific research of polymers.