OBJECTIVE: We wanted to introduce a new technique for superselective catheterization of arteries with preshaping of a micro-guide wire into a shepherd's hook form, and this is useful for superselection of small arteries branching at an acute angle from a large parent artery for the treatment of tumors and hemorrhages. MATERIALS AND METHODS: We developed a superselective catheterization technique by using preshaping of a micro-guide wire into a shepherd's hook form. We encountered six patients in our practice for whom we failed to catheterize the small tumor-feeding arteries that branched at an acute angle from wide parent arteries during chemoembolization of hepatocellular carcinoma; the parent arteries were the right inferior phrenic artery (n = 4) and the left gastric artery (n = 1) from the celiac axis with celiac stenosis due to compression by the median arcuate ligament and the proper hepatic artery from the gastroduodenal artery (n = 1) in a patient who had celiac axis occlusion with collateral circulation via the pancreaticoduodenal arcade from the superior mesenteric artery. In these consecutive six patients, we tested the usefulness of this new technique with employing preshaping of a micro-guide wire into a shepherd's hook form for superselective catheterization of targeted vessels. RESULTS: The target arteries were successfully catheterized and satisfactory transcatheter arterial chemoembolization was performed in all six patients. There were no significant complications such as arterial dissection. CONCLUSION: We developed a technique that is effective for superselection of vessels with preshaping of micro-guide wire into a shepherd's hook form, and we successfully applied it during chemoembolization of hepatocellular carcinoma. This technique can be useful for superselection of small arteries that branch from a large parent artery at acute angles for the treatment of tumors and hemorrhages