In most cases, persistent left superior vena cava (PLSVC) is asymptomatic and discovered accidentally. This case involves a 43-year-old male who underwent an emergency cadaveric liver transplantation. Postoperatively, the left internal jugular vein was cannulated using a sono-guided Seldinger technique in the intensive care unit. But the chest X-ray showed that the catheter followed the left paramediastinal course instead of crossing midline to the right to enter the superior vena cava. In consideration of the patient's status, an intra-arterial or extra-vascular placement could be excluded. For a diagnosis, we performed a bed-side transthoracic echocardiography with an agitated saline micro-bubble test. When agitated saline was injected through the catheter, the coronary sinus was initially opacified, and then the right atrium followed. In conclusion, we were able to make a diagnosis of PLSVC by a bedside test without radiation exposure.