The increasing incidence of aircraft cargo compartment fires in recent years has caused heavy losses and drawn attention to understanding the combustion process, especially under low pressure. The present paper aims at exploring the conditions of flashover at different pressures. Experiments were conducted in Guanghan (96 kPa) and Kangding (60 kPa), which are located at different altitudes. Five different sizes of pool fires were tested and smoke temperature and heat flux were measured for flashover criteria analysis. Corresponding simulations were performed using a commercial software FDS to examine the pressure effect on the flashover phenomenon and to validate the simulation results. The critical conditions for the onset of flashover in a 1/4 MPS compartment were found to be (1) an average upper layer temperature of about 450 °C at 96 kPa or about 550 °C at 60 kPa, and (2) radiant heat flux at floor level of about 10 to 15 kW/m2 at 96 kPa or 20 to 25 kW/m2 at 60 kPa. By using the average upper layer temperature as a criterion in modeling, a relatively accurate prediction of flashover onset time could be obtained at 96 kPa and a delay of about 25 s was found at 60 kPa.