To measure the fuel vapor concentration in an unsteady evaporating spray injected into nitrogen atmosphere, the exciplex-forming method, which produces spectrally separated fluorescence from the liquid and vapor phase, was applied in this study. Two experiments were conducted to investigate the qualitative and quantitative applicability of the technique in a high temperature and high pressure atmosphere during the fuel injection period. One is to examine the thermal decomposition of TMPD dopant at a high temperature and a high pressure nitrogen atmosphere during a short period of time. The other is to calibrate the relationship between fluorescence intensity and vapor concentration of TMPD at different vapor temperatures. And then, the qualitative measurement of fuel vapor concentration distributions in diesel sprays was made by applying the technique.