Hypergolic bipropellant of monomethylhydrazine (MMH) and nitrogen tetroxide (NTO) is extensively used in spacecraft propulsion applications and rocket engines. But studies on the chemical kinetic mechanism of MMH/NTO are limited. So, in this study by integrating the submechanisms of MMH decomposition, NTO thermal decomposition, MMH/NTO and intermediates, and small hydrocarbons, the comprehensive chemical mechanism of MMH/NTO bipropellant is proposed. The present chemical mechanism consists of 72 species and 406 elementary reactions. In two respects of ignition delay times and combustion flame temperatures, the present model has been validated against the theoretical calculation results and also compared with other kinetic models in the literature. The validations show that the predicted ignition delay times by the present kinetic model are highly consistent with the theoretical data and well describe the pressure-dependent characteristic. For combustion flame temperature, the present model also exhibits better predictions to the theoretical calculation results, which are also the same as the predictions by the MMH-RFNA model. Furthermore, the influences of initial temperature, chamber pressure, and NTO/HHM mass ratio (O/F) on the ignition delay time and combustion flame temperature are investigated. The auto-ignition behavior of MMH/NTO propellant is sensitive to initial temperature and chamber pressure, and the combustion flame temperature is more sensitive to the O/F. This study provides a detail chemical kinetics model for further mechanism simplification and combustion numerical simulation.