This case report describes the chemoembolization of a small hepatocellular carcinoma employing a lipiodol drug delivery system utilizing a novel arterial pathway. Because the target lesion was precariously located adjacent to the inferior heart border and the diaphragm, it was unsuitable for imaging-guided microwave ablation. To achieve chemoembolization, several intraprocedural adaptations were necessary, given the variant anatomy encountered and difficulty accessing the left gastric artery through a celiac artery approach. The left gastric artery was selected from a superior mesenteric artery approach through the pancreaticoduodenal arcade (Rio Branco's arcade). This case illustrates the importance of a mastery of the vascular anatomy and variants of hepatic arterial flow.