Image-level Weakly Supervised Semantic Segmentation (WSSS) has received increasing attention due to its low annotation cost. Class Activation Mapping (CAM) generated through classifier weights in WSSS inevitably ignores certain useful cues, while the CAM generated through class prototypes can alleviate that. However, because of the different goals of image classification and semantic segmentation, the class prototypes still focus on activating primary discriminative pixels learned from classification loss, leading to incomplete CAM. In this paper, we propose a plug-and-play Prototype-based Secondary Discriminative Pixels Mining (PSDPM) framework for enabling class prototypes to activate more secondary discriminative pixels, thus generating a more complete CAM. Specifically, we introduce a Foreground Pixel Estimation Module (FPEM) for estimating potential foreground pixels based on the correlations between primary and secondary discriminative pixels and the semantic segmentation results of baseline methods. Then, we enable WSSS model to learn discriminative features from secondary discriminative pixels through a consistency loss calculated between FPEM result and class-prototype CAM. Experimental results show that our PSDPM improves various baseline methods significantly and achieves new state-of-the-art performances on WSSS benchmarks. Codes are available at https://github.com/xinqiaozhao/PSDPM.