In order to improve engine thermal efficiency with reduced emissions, substantial studies have been carried out to improve the atomization and evaporation of fuel sprays, as well as fuel-air mixing in the engine cylinder. It has been found that flash-boiling spray is an effective way to achieve these goals. To further understand the evaporation characteristics and hear transfer phenomena between flash-boiling sprays and ambient gas, liquid temperature and vapor concentration of flash-boiling spray were measured quantitatively using laser induced exciplex fluorescence (LIEF) technique. The effects of fuel temperature, ambient pressure and superheated index (Pa/Ps) on the evaporation characteristics and heat transfer of fuel spray were investigated. The experimental results demonstrate that compared with non-flash-boiling spray, the rapid evaporation of flash-boiling spray leads to a higher vapor concentration along the center line. Meanwhile, the remarkable amount of energy absorbed from liquid phase of flash-boiling spray results in a faster liquid temperature decrease along the center line. When hot fuel is injected into cold environment, increasing fuel temperature leads to an increase of heat transfer from fuel spray to ambient gas because of the higher temperature difference between them. On the other hand, increasing ambient pressure decreases the evaporation rate of fuel spray due to the higher Pa/Ps. As such, the energy absorbed for fuel evaporation from liquid phase of spray is decreased, the heat transfer from fuel spray to ambient gas is increased.