The hydrothermal cracking of heavy oils, such as Canadian oil sand bitumen and Arabian heavy vacuum residue, as well as their model compound were performed over sulfided Ni/Al2O3 and NiMo/Al2O3 catalysts under 663~703 K and 6.0~8.0 MPa of hydrogen pressure in a batch autoclave reactor. According to the reaction mechanism of hydrothermal cracking, a small amount of free redical initiators, such as di-tert-peroxide, sulfur, etc., was added into the feed to generate free redicals at lower temperature, and obviously showed promotional effect on the conversion of hydrocarbons. The reaction mechanisms of hydrothermal cracking as well as the enhancing effect of initiators were studied by a probe reaction with 1-phenyldodecane as a model compound. The hydrothermal cracking of hydrocarbon proceeded via free redical mechanism and hydrogenating quench. The initiators might easily generate free redicals under reaction temperature, these redicals might abstract H from hydrocarbon molecule and reasonably initiate the chain reactions, therefore, promote the conversion of hydrocarbon even at lower reaction temperature.