Polysemy enables a single word to convey multiple related meanings, reflecting the conceptual and emotional aspects of the evolution of the senses. We introduce the first sense-level benchmark, SenseRel, for modeling semantic relations between word senses, uniting denotational and connotational aspects of meaning. SenseRel distinguishes denotational relations, such as generalization or metaphor, as well as two connotational dimensions: valence and arousal. We evaluate large language models (LLMs), GPT-4o, Llama 3.1, and DeepSeek, in zero-shot and fine-tuned settings. Results show that GPT-4o best aligns with human affective judgments, while a fine-tuned RoBERTa model excels at classifying denotational relations.