Background: Hepatocellular carcinoma (HCC) is the most common type of liver cancer, with 10–40% of cases involving portal vein tumor thrombosis (PVTT), leading to poor outcomes and a short survival. The effectiveness of PVTT treatment in patients with HCC is still controversial. Methods: This prospective dual-center study cohort comprised 60 patients with HCC and PVTT who underwent PVR-EPRFA-ST using a novel intravascular radiofrequency system followed by vascular stent placement across the PVTT stenosed segment under fluoroscopy guidance. Results: PVR-EPRFA-ST was technically and clinically successful in 54/60 (90%) and 37/54 (68.5%) patients, respectively. The mean tumor size, PVTT length, post-ablation luminal diameter, and median duration of the recanalized PV patency were 8.6 ± 3.4 cm, 4.1 ± 2.1 cm, 10.3 ± 1.8 mm, and 13.4 months. Higher technical and clinical success rates were associated with a longer survival (177 ± 17.3 days, HR: 0.3, 95%CI 0.12–0.71, p = 0.04; and 233 ± 18.3 days, HR: 0.14, 0.07–0.27, p < 0.001). A shorter survival was associated with Child–Pugh C (HR: 2.7, p = 0.04), multiple tumors (HR: 1.81, p = 0.03), and PVTT length (HR: 1.16, p = 0.04). Conclusions: PVR-EPRFA-ST was feasible and effective for the treatment of selected patients with PVTT, especially in patients with Child–Pugh A/B, single tumors, or a shorter PVTT length.