While the use of performance-based method for evaluating the behaviors of materials and fire protection systems becomes more widespread and effective, setting an objective criterion to judge fire behaviors becomes more and more important. However, flashover is reasonably assumed the best representation of critical conditions when the fire safety evaluation of buildings is considered. The experimental basis for working definitions of flashover and the equations for predicting the most common of the onset of flashover derived by the experts are presented. In addition, some of the numerical results deriving from the relative equations for the compartment fire that can be used to estimate flashover are presented.