The characteristics of combustion process in an internal combustion engine are affected by the mixing process between injected fuel and ambient gas. Therefore, it is necessary to understand the mixture formation process of diesel spray. In this study, the spray structure was visualized by the exciplex fluorescence method, which can provide the simultaneous 2-D images of vapor and liquid phase in inner spray. For accurate investigation, the liquid-phase images were recorded with a 35mm still camera and CCD camera. Consequentially, it could be confirmed that the high-concentration vapor phase is formed in the region of spray tip and the edge of the liquid phase where droplets exist in the evaporating diesel spray, and the formed vapor is spread by diffusion. Also, the distribution of vapor is determined by the motion of droplets that exist in the edge of the liquid phase and the spray-tip region.