Intravenous catheter placement in the healthy upper extremity is preferred for chemotherapy in patients with breast cancer. Common venous accesses are peripherally inserted central catheters (PICCs) and totally implantable intravenous port catheters (TIVPs). In this case, a patient with breast cancer had a history of infusion port placement through the left internal jugular vein, with ipsilateral innominate vein stenosis after placement. The patient was re-treated with a PICC placed ectopically through the left upper limb into the intrathoracic vein. After multidisciplinary consultation, a transfemoral PICC combined with intracavitary electrocardiography (IC-ECG) was performed to establish venous access. This case can assist PICC catheterization nurses in developing optimal venous access strategies tailored to the specific situations of patients in similar situations. Through adequate evaluations and optimal selection of venous access, the success rate of disposable catheterization can be improved, and the risk of complications reduced. A 53-year-old female with breast cancer had a history of infusion port, with ipsilateral innominate vein stenosis after placement. The patient was re-treated with a PICC placed ectopically through the left upper limb into the intrathoracic vein. An axial computed tomography (CT) image before totally implantable venous access port (TIVP) placement and An axial CT 103 days after TIVP placement shows diffuse stenosis of the left innominate vein, associated with infusion port placement through the left internal jugular vein. After multidisciplinary consultation, a transfemoral PICC combined with intracavitary electrocardiography (IC-ECG) was performed to establish venous access. The patient's lower limb PICC was left in place for 201 days with no complications, completing the full treatment cycle. This case presents a rare and insightful clinical scenario. For patients with a history of infusion port placement, particularly via the left internal jugular vein, careful analysis of the innominate vena cava and examination of chest wall vein exposure are essential to determining the optimal vascular access strategy.