The present study experimentally investigates the concentration distribution of liquid and vapor phase with different injection timings in the in-cylinder flow field of a optically accessible engine. The conventional MPI, DOHC engine was modified into DI gasoline engine. The images of liquid and vapor phases in the motoring engine were captured by using exciplex fluorescence method. Dopants used in this study were 2% fluorobenzene and 9% DEMA(diethyl-methyl-amino) in 89% solution of hexane by volume respectively. Two dimensional spray fluorescence images of liquid and vapor phases were acquired to analyze spray behaviors and fuel distribution in the in-cylinder flow field. Measurements were carried out fur four different injection timings, namely BTDC 270$^{circ}$, 180$^{circ}$, 90$^{circ}$, and 50$^{circ}$. Experimental results indicate that behaviors and distribution of vapor phase were largely affected by in-cylinder tumble flow, and mixture formation process was also greatly affected by in-cylinder flow at early injection mode and by ambient pressure at late injection mode.