A new type of modified phenolic resin/glass fiber composite is introduced. Phenolic resin was modified with 2% polyvinyl alcohol(PVA). Test specimens were prepared by mixing and molding. Fourier transform infrared spectroscopy (FTIR) was adopted to investigate its molecular structure. FTIR results showed that long aliphatic chain were introduced into the structure of PR, which could absorb the energy during load was applied on the composite. The toughing mechanism was investigated by comparing the impact strength, bending resistance, tensile strength with non-modified phenolic resin. Results shows that the impact strength of the modified PR/GF composite reaches 53.21 KJ/m2, which is almost 2 times more than that of pure PR/GF composite. Finally, the application of the modified PR/GF composite on shoes head was introduced.