The placement of large bore double-lumen catheters for hemodialysis (HD) is one of the most frequent procedures performed in HD patients. However, these procedures are associated with complications, the most common being catheter malposition. In this context, catheter deviation to the left superior intercostal vein (LISV) is a very uncommon malposition, which must be differentiated from intrathoracic extravascular catheter lodgment. We report a case of an adult male patient on hemodialysis who presented with a thrombosed arteriovenous fistula and requiring urgent HD. His past medical history included hemophilia, allergy to contrast media, and multiple previous central vein catheterizations. A non-tunneled HD catheter was placed without any difficulty in the left internal jugular vein. However, the arterial lumen failed to pull any blood with free flow in the venous lumen. A chest X-ray revealed a surprising finding. The malpositioned catheter was removed successfully without any complications.