The spray structures and distribution characteristics of liquid and vapor phases in non-evaporating and evaporating Gasoline Direct Injection (GDI) fuel sprays were investigated using Laser Induced Exciplex Fluorescence (LIEF) technique. Dopants were 2% fluorobenzene and 9% DEM A (diethyl-methyl-amine) in 89% solution of hexane by volume. In order to study internal structure of the spray, droplet size and velocity under non-evaporating condition were measured by Phase Doppler Anemometry (PDA). Liquid and vapor phases were visualized at different moments after the start of injection. Experimental results showed that the spray could be divided into two regions by the fluorescence intensity of liquid phase: cone and mixing regions. Moreover, vortex flow of vapor phase was found in the mixing region. About 5μn diameter droplets were mostly distributed in the vortex flow region. Higher concentration of vapor phase due to vaporization of these droplets was distributed in this region. Particularly, higher concentration of vapor phase and lower one were balanced within the measurement area at 2ms after the start of injection.