Central venous catheterization is widely regarded as a safe procedure by anesthesiologists and intensivists, but insertion complications and catheter malposition remain challenges for the clinicians performing central venous catheter (CVC) insertion. We report a case in which a right internal jugular CVC was inserted under ultrasound guidance and was found to be malpositioned after sternotomy into an anomalous posterior thymic vein. Therefore, we recommend confirming the correct position of CVC with transesophageal echocardiography if such is indicated for the perioperative period and emphasize the importance of a correct J-tip of the guidewire when placing a CVC.