The heat transfer problem of the atomized droplets during high velocity arc spraying (HVAS) was modeled and solved by a numerical method using a Fe-Al alloy, and the influences of several important process parameters on the heat transfer behaviors of the atomized droplets were analyzed. The results show that the initial cooling rates of different size droplets range from 105 to 107 K/s, thus producing the coating microstructure with the features of rapid solidification. The droplet size, atomization gas pressure and droplet superheat have great influences on the heat transfer behavior of the droplet. The droplet temperature and cooling rate are much sensitive to the droplet sizes, but insensitive to the atomization gas pressure and droplet superheat. It can be predicted that the properties of HVAS coatings will be improved by decreasing droplet size as well as increasing atomization gas pressure and droplet superheat in certain extents.