Porosity is considered as one of the most important indicators for the characterization of the comprehensive performance of thermal barrier coatings (TBCs). In this study, the ultrasonic technique and the artificial neural network optimized with the genetic algorithm (GA_BPNN) are combined to develop an intelligent method for automatic detection and accurate prediction of TBCs’s porosity. A series of physical models of plasma‐sprayed ZrO2 coating are established with a thickness of 288 μm and porosity varying from 5.71% to 26.59%, and the ultrasonic reflection coefficient amplitude spectrum (URCAS) is constructed based on the time‐domain numerical simulation signal. The characteristic features (f1, f2, Amax, ΔA) of the URCAS, which are highly dependent on porosity, are extracted as input data to train the GA_BPNN model for predicting the unknown porosity. The average error of the prediction results is 1.45%, which suggests that the proposed method can achieve accurate detection and quantitative characterization of the porosity of TBCs with complex pore morphology.