This case report discusses a 26-year-old woman with persistent left superior vena cava (PLSVC), incidentally discovered after successful left internal jugular vein catheterization for hemodialysis. Dialysis was conducted through this PLSVC for seven months without complications, suggesting its viability as a vascular access option when draining into the coronary sinus and right atrium. The report serves to raise awareness among nephrologists about the potential for using PLSVC for dialysis while underlining the importance of monitoring for complications such as arrhythmias.