Weakly Supervised Semantic Segmentation (WSSS) with image-level labels aims to achieve pixel-level predictions using Class Activation Maps (CAMs). Recently, Contrastive Language-Image Pre-training (CLIP) has been introduced in WSSS. However, recent methods primarily focus on image-text alignment for CAM generation, while CLIP's potential in patch-text alignment remains unexplored. In this work, we propose ExCEL to explore CLIP's dense knowledge via a novel patch-text alignment paradigm for WSSS. Specifically, we propose Text Semantic Enrichment (TSE) and Visual Calibration (VC) modules to improve the dense alignment across both text and vision modalities. To make text embeddings semantically informative, our TSE module applies Large Language Models (LLMs) to build a dataset-wide knowledge base and enriches the text representations with an implicit attribute-hunting process. To mine fine-grained knowledge from visual features, our VC module first proposes Static Visual Calibration (SVC) to propagate fine-grained knowledge in a non-parametric manner. Then Learnable Visual Calibration (LVC) is further proposed to dynamically shift the frozen features towards distributions with diverse semantics. With these enhancements, ExCEL not only retains CLIP's training-free advantages but also significantly outperforms other state-of-the-art methods with much less training cost on PASCAL VOC and MS COCO.