It has long been proposed that elevation of liver enzymes including alanine aminotransferase (ALT), aspartate aminotransferase (AST) and γ-glutamyltransferase (GGT) may be associated with insulin resistance (IR). In the present study, we aimed to investigate the association of the above mentioned liver enzymes with IR by using hyperinsulinemic euglycemic clamp, as well as their relationship with individual component of metabolic syndrome (MetS) in 95 newly diagnosed type 2 diabetes (T2DM) Chinese patients. All the diagnosed patients did not use drugs for treatment of diabetes or dyslipidemia previously and were divided into IR and non-IR groups. The results showed that IR group had significantly higher ALT, AST, and GGT (P<0.01, P<0.01, and P<0.05, respectively) compared with non-IR group. According to the individual MetS component, ALT and AST were significantly increased in patients with high blood pressure compared with those without (both P<0.001); ALT and GGT were increased in patients with high triglyceride (P<0.05 and P<0.01); AST was increased in patients with central obesity (P<0.05). In correlation analysis, a significant association was found between the three liver enzymes and clamp insulin sensitivity index (all P<0.001). In the linear regression analysis, ALT was the determinant of clamp ISI, independent of age, sex, BMI, and fasting and OGTT 2 h plasma glucose (P<0.0001). In conclusion, liver enzymes, especially ALT, were significantly associated with IR according to direct clamp assessment, which were independent of the traditional risk factors in diabetic patients; and individual liver enzymes may have different relationship with individual component of MetS.