A persistent left-sided superior vena cava (PLSVC) is the most frequent abnormality of the venous system; however, it is not a very well-known variation among physicians. Herein we report the case of a patient with a PLSVC who was diagnosed after central venous catheterization (CVC). An 80-year-old man was admitted to the emergency room with cardiopulmonary arrest. After the return of spontaneous circulation, CVC was blindly performed from the left jugular vein without any complications. However, routine chest X-ray after catheterization revealed that the catheter was moving down directly to the left heart. Thoracic computed tomography showed the right brachiocephalic vein draining into the left brachiocephalic vein and forming the left superior vena cava in front of the aortic arch. The left superior vena cava merged into the right atrium after crossing the left pulmonary artery. CVC is widely used in clinical practice, and therefore clinicians should be aware of possible variations in central veins, particularly during blind catheterization.