The synthesis of cationic waterborne polyurethane used poly tetramethylene glycol (PTMG), 4,4'methylenedicylohexyldiisocyanate (H12MDI) and N-methyl diethanolamine (N-MDEA) as major materials to synthesize polyurethane and then neutralize with acetic acid. The reaction product was dispersed in water. Cationic waterborne polyurethane was formed by self-emulsification. The hybrid film formed by blending polyurethane with silk fibroin was found to have the cool-feeling effect while the hybrid film formed by blending polyurethane with chitosan was found to have the antibacterial effect. From DMA simulated peaks, as the addition fraction of silk fibroin or chitosan increases, the hybrid film of PU blended with silk fibroin or chitosan has the lower glass transition temperature for soft and hard segments (Tg(s), Tg(h)) than that of pure PU. From TGA, the decomposition temperature (Td) of the hybrid film of PU with silk fibroin or chitosan is decreased. The stress-strain curves of the hybrid films reveal that the tensile strength is increased but the elongation is decreased, as the addition fraction of silk fibroin increases. The Q-max test shows the addition of silk fibroin can increase the cool feeling value. The addition of chitosan can increase the antibacterial effect of the hybrid film.