Objective. To explore the predictive value of magnetic resonance imaging (MRI) with serum lectin-reactive alpha-fetoprotein (AFP-L3) for liver cancer recurrence after percutaneous radiofrequency ablation (RFA). Methods. This study included 94 liver cancer patients admitted for RFA treatment and 82 healthy subjects. MRI was performed to record the apparent diffusion coefficient (ADC). The serum concentrations of AFP-L3 were quantified in all participants. The correlation of the AFP-L3 serum level and ADC value with clinical efficacy following RFA was analyzed. Moreover, the prognostic factors affecting liver cancer recurrence were analyzed, as well as the predictive effect of the ADC value and AFP-L3 on liver cancer recurrence. Results. The serum AFP-L3 level was higher in liver cancer patients than the healthy controls with a lower ADC value. Besides, the patients with tumor residuals had lower ADC values and higher serum AFP-L3 levels than those with complete ablated tumor. The combined detection of the ADC value and serum AFP-L3 level had a sensitivity of 87.50% and a specificity of 87.18% for diagnosing complete ablation after RFA treatment. The number of tumor nodules, tumor diameter, AFP, AFP-L3, and the presence of liver cirrhosis are all independent risk factors for liver cancer recurrence within one year. Meanwhile, the combined detection of the ADC value and serum AFP-L3 level had a good predictive effect on liver cancer recurrence with the sensitivity of 92.86% and a specificity of 69.62%. Conclusion. The ADC values combined with serum AFP-L3 detection had good predictive effects on complete ablation and recurrence of liver cancer after RFA treatment.