Central venous catheterization through a subclavian approach is indicated for some special purposes but it may cause many complications such as infection, bleeding, pneumothorax, thrombosis, air embolization, arrhythmia, myocardial perforation, and nerve injury. A case involving a mistaken central venous catheterization into the right vertebral artery through the subclavian artery is presented. A 33-year-old man who had deteriorated mentality after head injury underwent an emergency craniotomy for acute epidural hematomas on the right frontal and temporal convexities. His mentality improved rapidly, but he complained of continuous severe pain in the right posterior neck even though he had no previous symptom or past medical history of such pain. Three-dimensional cervical spine computed tomography (3D-CT) was performed first to rule out unconfirmed cervical injuries and it revealed a linear radiopaque material intrathoracically from the level of the 1st rib up to the level of C6 in the right vertebral foramen. An additional neck CT was performed, and the subclavian catheter was indwelling in the right vertebral artery through right subclavian artery. For the purpose of proper fluid infusion and central venous pressure monitoring, the subclavian vein catheterization had been performed in the operation room after general anesthesia induction before the craniotomy. Sufficient anatomical consideration and prudence is essential because inadvertent arterial cannulation at a non-compressible site is a highly risky iatrogenic complication of central venous line placement.