Characterization of the spray angle, penetration, and droplet size distribution is important to analyze the spray and atomization quality. In this paper, the spray structure development and atomization characterization of two naphtha fuels, namely light naphtha (LN) and whole naphtha (WN) and two reference fuel surrogates, i.e. toluene primary reference fuel (TPRF) and primary reference fuel (PRF) were investigated using a gasoline direct injection (GDI) fuel injector. The experimental setup included a fuel injection system, a high-speed imaging system, and a droplet size measurement system. Spray images were taken by using a high-speed camera for spray angle and penetration analysis. Sauter mean diameter, Dv(10), Dv(50), Dv(90), and particle size distribution were measured using a laser diffraction technique. Results show that the injection process is very consistent for different runs and the time averaged spray angles during the measuring period are 103.45°, 102.84°, 102.46° and 107.61° for LN, WN, TPRF and PRF, respectively. The spray front remains relatively flat during the early stage of the fuel injection process. The peak penetration velocities are 80 m/s, 75 m/s, 75 m/s and 79 m/s for LN, WN, TPRF and PRF, respectively. Then velocities decrease until the end of the injection and stay relatively stable. The transient particle size and the time-averaged particle size were also analyzed and discussed. The concentration weighted average value generally shows higher values than the arithmetic average results. The average data for WN is usually the second smallest except for Dv90, of which WN is the biggest. Generally the arithmetic average particle sizes of PRF are usually the smallest, and the sizes does not change much with the measuring locations. For droplet size distribution results, LN and WN show bimodal distributions for all the locations while TPRF and PRF shows both bimodal and single peak distribution patterns. The results imply that droplet size distribution is skewed to the larger side for locations close the axis and is skewed to the smaller side for distance away from the axis.