Peripherally inserted central venous catheter (PICC) lines have become a frequently used method of intravenous access for long-term administration of antibiotics, chemotherapy, and parenteral nutrition. Catheter-related complications involving the arterial tree are rare. We report a case of a 25-year-old woman with a history of difficult PICC line placement that presented with an arteriovenous fistula in the left arm. Duplex ultrasound confirmed the diagnosis of a brachial artery-to-brachial vein arteriovenous fistula (AVF), and the patient underwent surgical repair. To our knowledge, this is the first reported case of an AVF resulting from PICC line placement. Correction of AVF is indicated to alleviate symptoms as well as to prevent future complications.