Objective. To evaluate the feasibility and safety of portal vein stenting (PVS) combined with 125 I particle chain implantation and sequential arsenic trioxide (As 2 O 3 ) for the treatment of hepatocellular carcinoma (HCC) with portal vein tumour thrombus (PVTT) by transcatheter arterial chemoembolization (TACE). Methods. From January 2015 to January 2018, the clinical data of 30 patients with HCC complicated by PVTT were retrospectively analysed (26 men and 4 women). e laboratory examinations, incidence of adverse events, cumulative survival rate, and stent patency were analysed for all enrolled patients. Results. e success rate of interventional treatment in all patients was 100%. e results of the laboratory tests before and 1 week after surgery showed that the mean concentrations of alanine aminotransferase (ALT) and aspartate aminotransferase (AST) decreased from 50.9 U/ L ± 25.8 to 41.8 U/L ± 21.6 (P < 0.001) and 57.6 U/L ± 19.9 to 44.2 U/L ± 26.1 (P < 0.001), respectively. No complications in grade 3 or higher according to the Common Terminology Criteria for Adverse Events (CTCAE) were observed. e cumulative survival rates at 3, 6, 9, and 12 months were 83.1%, 69.2%, 43.7%, and 31.2%, respectively, while the patency rates of the stents were 83.3%, 80.0%, 52.2%, and 38.3%, respectively. Of the 30 deaths during the follow-up period, 16 patients died of liver failure, 8 died of gastrointestinal bleeding, 3 died of lung metastasis, 2 died of brain metastases, and 1 died of heart failure because the tumour invaded the atria. Conclusion. PVS combined with 125 I particle chain implantation followed by TACE with As 2 O 3 is safe and feasible for patients with PVTT. e long-term efficacy of this treatment needs to be further studied.