In consideration of droplet–film impaction, film formation, film motion, bubble boiling (both wall nucleation bubbles and secondary nucleation bubbles), droplet–bubble interaction, bulk air convection and radiation, a model to predict the heat and mass transfer in spray cooling was presented in this paper. The droplet–film impaction was modeled based on an empirical correlation related with droplet Weber number. The film formation, film motion, bubble growth, and bubble motion were modeled based on dynamics fundamentals. The model was validated by the experimental results provided in this paper, and a favorable comparison was demonstrated with a deviation below 10%. The film thickness, film velocity, and non-uniform surface temperature distribution were obtained numerically, and then analyzed. A parameters sensitivity analysis was made to obtain the influence of spray angle, surface heat flux density, and spray flow rate on the surface temperature distribution, respectively. It can be concluded that the heat transfer induced by droplet–film impaction and film-surface convection is dominant in spray cooling under conditions that the heated surface is not superheated. However, the effect of boiling bubbles increases rapidly while the heated surface becomes superheated.