The syntheses of cardanol-glycols (CGs) and CG-based polyurethane (CGPU) films have been investigated. The characterization of CGs and CGPU films were determined by IR, H-1-NMR spectra as well as a swelling test and DSC studies. The increase of molecular weight of glycols leads to a decrease of cardanol content in CGPUs and hence decreases crosslinking density of the films, which strongly affects the swelling property and glass transition temperature. The autooxidation-polymerization of CGPUs through the double bonds of the cardanol side chain, catalyzed by cobalt salt, resulting the crosslinking films was also discussed.