We experienced a case in which a central venous catheter (CVC) was misplaced into the wrong vein, which was mistaken for the internal jugular vein (IJV), identified by chest x-ray and ultrasound. The vertebral vein passes through the transverse foramina from the atlas to the 6th cervical vertebra. After exiting the transverse foramen of the 6th vertebra, the vein subsequently runs anterolateral to the vertebral artery and posterior to the IJV and drains the innominate vein. In this case, chest x-ray and ultrasound revealed that the inserted CVC had a course very similar to the vertebral vein. The misplacement of a CVC into the vertebral vein might occur from excessive rotation of the patient's head, which leads to alterations in the cervical vascular anatomy, and from deep insertion of the puncture needle. Therefore, it is advised, for safe CVC insertion, to minimize a patient's head rotation and to make use of ultrasound when the anatomical structures cannot be clearly identified.