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Background Transarterial chemoembolization using microspheres is a new treatment option for patients with hepatocellular carcinoma. Objective To assess the effectiveness of this technique, in terms of tumor response and overall survival rates, and to assess the procedure’s safety. Setting A General University Hospital in Spain. Methods Single-center retrospective observational study. The cohort included all patients treated between October 2006 and April 2010. Effectiveness was determined by the tumor response rate (using modified RECIST and EASL criteria) and overall survival. Safety was assessed according to the Common Terminology Criteria for Adverse Events. Main outcome measure Tumor response rate, overall survival and safety of transarterial chemoembolization in patients with hepatocelular carcinoma. Results 53 patients were treated (81.1 % men, median age 65). Baseline characteristics 98.1 % had cirrhosis, 75.5 % Child-Pugh Class A, 71.7 % Okuda I, and 94.3 % were ECOG 0. 43.4 % were waiting for a liver transplant and 56.6 % were given the treatment as a palliative measure. Eighty-one procedures were carried out, with a median of 1 per patient [1–5]. Four weeks after treatment, the objective response rate was 87.5 % and the complete response rate was 62.5 %. Median survival was 735 days (CI 95 %: 351.9–1118.1). The 1, 2 and 3-year overall survival rates were 65.4, 50.9 and 42.5 %, respectively. 71.7 % of patients experienced post-embolization syndrome, with grade 1 abdominal pain as the most frequent symptom (37.7 %). Conclusion This study provides new evidence of the safety and effectiveness of transarterial chemoembolization using doxorubicin-loaded microspheres for the treatment of hepatocellular carcinoma in patients who are not eligible for other treatments, or as a bridging treatment in patients on the liver transplant waiting list.