We herein describe a 48-year-old man who developed acute painful ophthalmoplegia of the right eye for 5 days. Magnetic resonance imaging of the brain with contrast detected a contrast-enhancing lesion in the right cavernous sinus (CS) and petrous apex. Tolosa-Hunt syndrome was suspected initially, but later he was diagnosed as CS metastasis from hepatocellular carcinoma (HCC). To the best of our knowledge, only nine similar cases have been reported in the literature. We would like to remind clinicians to consider the possibility of CS metastasis in patients with primary HCC, who present with acute painful ophthalmoplegia.