Spray structures and penetration lengths of Gasoline, M85, E85, and LPG by a GDI 6-hole fuel injector were examined in a constant volume chamber. The chamber pressure was controlled at 0.1 MPa and 0.9 MPa. The effects of fuel injection pressure and chamber pressure on the spray structures and penetration lengths were investigated using the 2-dimensional Mie scattering technique. It was found that the sprays developed linearly till ASOI 1.7ms after start of injection and vortices were happened around jets on the way of spray development. And the high chamber pressure, 0.9 MPa kept the fuel sprays development down and the penetration length was reduced to about 55% compared with that of 0.1 MPa. In additions high pressure of fuel injection, 12 MPa increased the spray penetration length more about 7~10% than that of 7 MPa.