Objective To investigate the diagnostic value of alpha-fetoprotein (AFP),α-L-fucosidase(AFU),gamma-glutamyltransferase(GGT),alkaline phosphatase (ALP) and carbohydrate antigen 19-9(CA19-9) in the diagnosis of primary hepatocellular carcinoma(PHC).Methods Seventy-eight PHC patients as PHC group,76 patients with other liver diseases as other liver diseases group and 60 healthy volunteers as control group.The level of serum AFP,AFU,GGT,ALP,CA19-9 and positive rate in each group were compared.Results The level of AFP,AFU,GGT,ALP,CA19-9 in PHC group were (276.3 ±72.6)μg/L,(63.1 ± 11.7) U/L,(268.5 ±57.2) U/L,(293.4 ±61.7) U/L and (56.9 ± 12.5) μg/L,in other liver diseases group were (81.6 ± 12.1) μg/L,(28.3 ±7.3) U/L,(54.9 ±7.8) U/L,(116.5 ± 23.8) U/L and (27.8 7.1) μ g/L,in control group were (13.8 ± 2.7) μ g/L,(12.6 ± 3.9) U/L,(12.3 ± 3.2) U/L,(47.2 ± 11.3) U/L and (12.9 ± 3.4) μ g/L.The level of above index in PHC group and other liver diseases group were significantly higher than those in control group,while the level of above index in PHC group were significantly higher than those in other liver diseases group (P ＜ 0.01 or ＜ 0.05).The positive rate of AFP,AFU,GGT,ALP,CA19-9 in PHC group were 62.8％(49/78),79.5％(62/78),83.3％ (65/78),85.9％ (67/78),66.7％ (52/78),and significantly higher than those in other liver diseases group[31.6％(24/76),32.9％(25/76),27.6％(21/76),22.4％(17/76),15.8 ％(12/76)].The positive rate of AFP in control group was 0,the positive rate of AFU,GGT,ALP,CA19-9 in control group were 1.7％ (1/60),3.3％ (2/60),1.7％ (1/60),8.3％ (5/60),which significantly lower than those in other two groups.The positive rate of combined detection in PHC group was 100.0％(78/78),which significantly higher than that in other liver diseases group [40.8％(31/76)] and control group[8.3％(5/60)](P＜ 0.01).Conclusion The combined detection of AFP,AFU,GGT,ALP,CA19-9 in PHC diagnosis has a higher sensitivity,and thus to make an early diagnosis and early treatment for PHC.