Flashover is the rapid transition to a state of total surface involvement in a fire of combustible material within an enclosure fire, which is the most serious and fatal event in building fires. Although previous studies have provided quantitative and qualitative standards for flashover, the criteria of flashover were normally based on the independent measurement of experimental parameters and phenomena rather than the underlying physical reasons, resulting in a lack of mutual relationships between these criteria and the inability to reflect physical mechanisms. Moreover, the flashover criteria vary for different compartment fire fuels, which directly affects the calculation of compartment fire theory. This work was performed to provide a unified principle on the criteria of flashover based on the thermal equilibrium theory. The critical conditions for flashover are quantitatively developed by establishing a partial differential equation for the energy generation rate and energy loss rate with respect to the temperature inside the compartment. Moreover, based on the partial differential equation, inequalities were established for the relationship between the temperature of the hot gas and the heat flux of the floor at the onset of flashover, which was validated by the compartment experiment data. It was found that due to differences in emissivity and net heat transfer rate, at the onset of flashover, the hot gas temperature and the radiation heat flux at the floor were different for different fuels, and a high hot gas temperature does not necessarily indicate a high radiation heat flux at the floor.