Single-excite dual-fluorescence PLIF was applied to a diesel spray of a two-component fuel, the components of which have different boiling points. The spray was formed by injecting fuel into a constant-volume vessel under high-temperature, high-pressure conditions. The fluorescence emitted from the two tracers for the fuel was optically separated to measure the concentration of each component. Mixture formation was investigated based on the concentration distributions of each fuel component. The fuel concentration was derived based on the change in fluorescence intensity due to temperature and the assumption of adiabatic mixing of fuel and the surrounding fluid. The variation in the mixture distribution due to differences in the vaporization characteristics was investigated, and the results revealed that the two components have similar distribution. The concentration of the high-boiling-point component increased upstream region in a spray.