Phantom limb syndrome (PLS) is a condition that occurs in amputee patients that has a wide array of different treatment approaches. We present the case of a patient diagnosed with complex regional pain syndrome (CRPS) of the right upper limb secondary to polytrauma with complete brachial plexus injury, who, after being subjected to multiple successful therapies, was finally taken to amputation. Later, he developed a painful PLS that was difficult to manage, which was treated with a stellate ganglion block (SGB), achieving a significant decrease in pain. This article aims to present a case in which a SGB was used as an adjunct to control acute postoperative PLS in a patient with previous sensitization due to CRPS. The SGB, in this case, performed with local anesthetic plus corticosteroid, constitutes a useful therapeutic alternative for intense postoperative pain in PLS, achieving adequate pain relief without adverse effects. However, its routine use as in acute postoperative pain still lacks sufficient evidence for complete support, therefore we urge the scientific community to undertake more in-depth research concerning this topic in order to create clear guidelines and recommendations.