Optimal design of modern direct injection spark-ignition engines depends heavily on the characteristics and distribution of the fuel spray. This study was designed to investigate changes in the spray properties due to fuel volatility and operating conditions using a firing optically-accessible engine with planar laser-induced fluorescence (PLIF) imaging. The results show that the spray structure changes not only with ambient gas density, which is often measured, but also with fuel temperature and volatility. As ambient pressure decreases and fuel temperature increases, the volatile ends of multi-component fuels evaporate quickly, disrupting the spray structure and producing a vapor core along the axis of the spray. Beyond a certain point, evaporation is rapid enough to expand the initial cone angle of the spray while causing a decrease in the overall spray width. The axial and radial penetration of these sprays was found to depend on the fuel temperature, the ambient density, and vapor generation.