Objective To study the effects of radiofrequency ablation combined with transcatheter arterial chemoembolization (TACE) on liver function and immune function of patients with primary liver cancer. Methods 90 patients with primary liver cancer admitted to Wenchang People’s Hospital from June 2017 to June 2020 were selected and acted as research objects, they were divided into the control group (45 cases) and the observation group (45 cases) according to the random number table method. Patients in the control group received TACE treatment, patients in the observation group were treated with radiofrequency ablation on the basis of the control group, patients in the two groups were followed up for 3 months after treatment. The clinical efficacy 3 months after treatment, the levels of liver function indexes and immunoglobulin A (IgA), immunoglobulin G (IgG), immunoglobulin M (IgM) before and 1 month after treatment, and the quality of life 3 months after treatment of patients in the two groups were compared. Results The objective remission rate and disease control rate of the observation group were higher than those of the control group; compared with before treatment, the levels of total bilirubin (TBiL), aspartate aminotransferase (AST), and alanine aminotransferase (ALT) of patients in the two groups 1 month after treatment decreased, and the observation group was lower than the control group; compared with before treatment, the serum IgA, IgG, and IgM levels of patients in the two groups 1 month after treatment increased, and the observation group was higher than the control group; compared with before treatment, the life quality scores of social function, physical function, emotional function of patients in the two groups 3 months after treatment increased, and the observation group was higher than the control group; compared with before treatment, the pain scores of patients in the two groups 3 months after treatment decreased, and the observation group was lower than the control group (all P<0.05). Conclusion Radiofrequency ablation combined with TACE can significantly alleviate the clinical symptoms of patients with primary liver cancer, improve liver function and immune function of patients, and can enhance the patients’ quality of life, relieve pain, the treatment effect was remarkable.