In the chemical industry, fault diagnosis is a challenging task due to the complexity of chemical equipment. This paper proposes a machine learning-based approach to achieve the goal of fault diagnosis. First, in order to reduce the impact of redundant features, support vector machine recursive feature elimination (SVMRFE) is used to select important features. The trained probabilistic neural network (PNN) is then used for fault diagnosis. Considering that the diagnostic performance is affected by its hidden layer element smoothing factor (sigma), the modified bat algorithm (MBA) is used to optimize the PNN to obtain optimal global parameter values. The MBA adopts a better optimization mechanism than the basic algorithm and achieves excellent global convergence. It can globally optimize the smoothing factor, which effectively improves the fault diagnosis ability of the PNN. During the testing of the Tennessee Eastman (TE) process data set, we evaluate the performance of the proposed model by comparing the F-1-score and accuracy of the different methods. The charts provided describe the fault diagnostic results and classification for the different models. The results indicate that the MBA has a better optimization ability than other traditional optimization algorithms. At the same time, the combination method proposed in this paper is also superior to others and can significantly improve the accuracy of TE process fault diagnosis.