Because an injected spray development process consists of impinging and free spray in the diesel engine, it is needed to analyze the impinging spray and free spray, simultaneously, in order to study the diesel spray behavior. To dominate combustion characteristics in diesel engine is interaction between injected fuel and ambient gas, that is, process of mixture formation. Also it is very important to analyze liquid and vapor phases of injected fuel on the investigation of mixing process, respectively and simultaneously. Therefore, in this study, the behavior characteristics of the liquid phase and the vapor phase of diesel spray was studied by using exciplex fluorescence method in high temperature and injection pressure field. Finally, it can be confirmed that the distribution of vapor concentration is more uniform in the case of the high injection than in that of the low injection pressure.