Duodenocaval fistula (DCF) is a rare entity which is sparsely described in the literature. Few etiologies have been listed including chemoradiation therapy. Early recognition may reduce the high mortality rate. We describe the case of a 63-year-old woman with a history of stage III ovarian cancer treated with cytoreductive surgery and adjuvant chemotherapy, including bevacizumab, who presented to the hospital because of fresh blood per rectum. One month earlier, the patient was admitted to the intensive care unit because of hemorrhagic shock secondary to a necrotic duodenal ulcer and was treated with cauterization. The patient was stable when discharged home, however, she was readmitted to the hospital because of hematemesis and hematochezia and was again in hemorrhagic shock for which the patient was urgently transfused. An abdominal computerized tomography (CT) angiography demonstrated locules of air within the intrahepatic and infrahepatic inferior vena cava (IVC), as well as evidence of communication with the duodenal lumen, and a thrombus within the IVC. The patient was evaluated by the surgical oncology and vascular teams, who deemed the patient inoperable. Our case describes ovarian malignancy, treated by radiation, leading to duodenitis, with subsequent ulcer formation. The co-administration of bevacizumab delayed gastric healing and promoted ulcer perforation favoring fistula formation.