Visualization experiments are carried out to investigate the atomization characteristics of R1336mzz flash spray cooling. The influences of superheat, spray distance, and nozzle orifice diameter on spray cooling performance are analyzed experimentally. As the superheat increases, finer droplets and thinner liquid film are observed; this is helpful to improve the two-phase heat transfer efficiency. Enlarging atomization angle under high superheat is also observed for flash spray cooling, and it benefits for reducing the spray distance. It can be found that when the inlet superheat is 19.8°C and the spray distance is 6 mm, the critical heat flux (CHF) reaches 251 W/cm2 and the maximum heat transfer coefficient (HTC) reaches 37.4 kW/(m2 °C), which are 55% and 11.6% higher than those when the inlet subcooling is 6.9°C and the spray distance is 12 mm, respectively. Using flash spray reduces the spray distance, which benefits for designing compact spray cooling device. In addition, the nozzle orifice diameter has great influence on the cooling performance of flash spray, and the choice of the nozzle depends on the superheat. This study provides a physical insight into the heat transfer enhancement in flash spray cooling.