Stellate ganglion block is frequently effective on the pain of head and upper extremities. However, if the degree and duration of pain relief does not increase with repeated blocks, we may consider the neurolytic procedure on the stellate ganglion. A patient sufferring from the pain in the region of ophthalmic branch of left trigeminal nerve and left eyeball region had been treated with stellate ganglion block. In spite of repeated blocks, the degree and duration of pain relief did not increase. We performed the radiofrequency thermocoagulation of stellate ganglion at the operation room under fluoroscopy. Patient got pain relief immediately after the procedure without any remarkable complication except a mild ptosis, which was shown before the procedure. We may give priority to radiofrequency thermocoagulation for stellate ganglion neurolysis due to its simplicity and safty.