The effects of change in injection pressure on spray structure in high temperature and pressure field have been investigated. The analysis of liquid and vapor phases of injected fuel is important for emissions control of diesel engines. Therefore, this work examines the evaporating spray structure using a constant volume vessel. The injection pressure is selected as the experimental parameter, is changed from 400 bar to 800 bar by using a common rail injection system. Also, we conducted simulation study by modified KIVA-II code. The results of simulation study are compared with experimental results. The images of liquid and vapor phase for free spray were simultaneously taken by exciplex fluorescence method. As experimental results, the vapor concentration of injected fuel is leaner due to the increase of atomization in the case of the high injection pressure than in that of the low injection pressure. The calculated results obtained by modified KIVA-II code show good agreements with experimental results.