The effect of hydrogen embrittlement on the fracture toughness of titanium alloy with different surface modifications was investigated. Disk shape compact tension spectimens were first treated with different hard layers, then hydrogen charged into the substrate by electrochemical method. GDS, SEM, and X-ray diffractometry were applied to analyze the surface characteristics. The results revealed that as-received titanium alloy decreased with the increase of hydrogen charging time. Fracture toughness of the alloy after plasma nitriding or ion implantation decreased as well after cathodic charging, but alloy coated with CrN film, fracture toughness retained even after hydrogen charging for 144 hours. Obviously, hydrogen permeation was effectively retarded by the CrN film, but was at the sacrifice of the CrN film itself.