Roll-to-Roll (R2R) processing is a common processing method for flexible photoelectric film materials. Due to the physical properties of the materials, the change in the performance of the R2R processing equipment can easily cause deformation of the flexible film material, it is particularly important to predict the performance degradation of the processing equipment. Based on the accuracy and real-time requirements of performance degradation prediction, a PTS-FNN model for performance degradation prediction was proposed in this paper, which combines the Possibilistic C-Means (PCM) fuzzy clustering and Takagi–Sugeno Fuzzy Neural Network (TS-FNN). We also studied the PCM classification algorithm of input data of PTS-FNN model, the predecessor network of TS-FNN prediction model and the construction method of post-component network. Finally, the implementation process of PCM classification algorithm and TS-FNN prediction model were given. The R2R processing equipment health prediction experiment system was built and the PTS-FNN model experiment was carried out. The experimental results showed that the training time of PTS-FNN model was 50.37% less than the standard TS-FNN prediction model. The prediction accuracy increased by 5.48%, and the PTS-FNN had no error in the judgment of state 1 and state 4.