Thermoelectric generator (TEG) has important applications in automotive exhaust waste heat recovery. The Back propagation neural network (BP) can predict the electrical generating performance of TEG efficiently and accurately due to its advantage of being good at handing nonlinear data. However, BP algorithm is easy to fall into local optimum, and its training data usually have deviation since the data are obtained through the simulation software. Both of the problems will reduce the prediction accuracy. In order to further improve the prediction accuracy of BP algorithm, we use the genetic algorithm (GA) to optimize BP neural network by selection, crossover, and mutation operation. Meanwhile, we create a TEG for the heat waste recovery of automotive exhaust and test 84 groups of experimental data set to train the GA−BP prediction model to avoid the deviation caused by the simulation software. The results show that the prediction accuracy of the GA−BP model is better than that of the BP model. For the predicted values of output power and output voltage, the mean absolute percentage error (MAPE) increased to 2.83% and 2.28%, respectively, and the mean square error (MSE) is much smaller than the value before optimization, and the correlation coefficient (R2) of the network model is greater than 0.99.