This article presents an experimental and CFD simulation investigation and analysis on temperature evolution and flame behavior inside compartment with a ceiling vent under ambient wind. Experiments were conducted employing a reduced-scale model containing a cubic fire compartment with a ceiling vent under the external wind generated by a wind tunnel. The temperature of windward and leeward inside compartment as well as the flame behavior were recorded for various vent dimensions, heat release rates and wind speeds for a total of 720 test conditions. Results show that there are two types of fire behavior regimes inside the compartment for relatively small- (Bernoulli flow regime) or large vents (oscillatory exchange flow regime). With a relatively small vent, the flame is located at the center of compartment and the temperatures of windward and leeward are almost the same with or without the ambient wind. Then the flame turns to extinct due to lack of oxygen with increasing of fuel supply. However, with a relatively large vent, there is a flame transition from windward to leeward accompanied by the transition of temperature distribution with increasing of fuel supply when subject to ambient wind. Such extinction and transition mechanisms are interpreted by the aid of CFD simulation of global equivalence ratio and flow/oxygen field inside compartment. The critical heat release rate for the occurrence of flame transition decreases with raising wind speed while increases with vent size. Their complex dependence is found to be well represented in terms of a non-dimensional heat release rate as a function of the wind Froude number, employing the vent area-equivalent characteristic diameter as length scale. These new findings facilitate the understanding of the compartment fire evolution with a ceiling vent subject to ambient wind.