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Chemical neurolysis of the brachial plexus and paravertebral space have been sparsely reported. This case involves a patient with refractory pain from stage IV breast cancer, characterized by severe discomfort in the right axilla, shoulder, and pectoral region. A diagnostic block with local anesthetics at T2 and T4 paravertebral spaces and interscalene brachial plexus provided 80% pain relief for 12 hours. Subsequent phenol neurolysis at the same sites achieved 70% sustained pain relief and reduced opioid use for 4 weeks. Chemical neurolysis remains a critical tool in the palliative care arsenal, offering substantial relief in the final stages of life.