In this paper, a mathematical model based on graph theory is proposed to calculate the heat distribution of LED lights’ convective cooled heat sink. First, the heat and mass transfer process of a single fin under moisture environment is analyzed. Then, the heat transfer process is characterized by a digraph, defining fins and joints of a heat sink as edges and vertices in graph theory. Finally, the whole heat transfer process is described by two criteria achieved based on graph theory. Therefore, the temperature-heat calculation equations of the whole heat sink are deduced. The accuracy of this model is verified by testing the junction temperature of different LED chips mounted on the same heat sink under moisture environment, and the relative errors between the calculated value and the experimental data are all within 5%, and it is also concluded from the model that heat sinks with an identical heat digraph but different types have close cooling performance and are verified by two typical heat sinks, cylindrical heat sink and rectangular plate-fin heat sink, under the same conditions. The mathematical model based on group theory developed in this paper combined with computer technology is convenient for the performance analysis among a large number of heat sink fin arrangement schemes.