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Objective Coronary artery calcification (CAC) is positively and independently associated with cardiovascular disease (CVD) in patients undergoing maintenance hemodialysis (MHD). Insulin resistance is independently associated with CAC and is an important risk factor for CVD. The triglyceride–glucose (TyG) index is a reliable biomarker of insulin resistance. This cross-sectional, observational study aimed to investigate the relationship between the TyG index and CAC in asymptomatic non-diabetic patients undergoing MHD. Methods The quantitative coronary artery calcification score (CACS) was calculated and expressed using the Agatston score. The TyG index was calculated as ln [fasting triglyceride (mg/dL) × fasting glucose (mg/dL)/2]. Multiple Poisson regression analysis, Spearman correlation analysis, and receiver operating characteristic (ROC) curves were used to investigate the relationship between the TyG index and CAC. Results The 151 patients were divided into three groups according to the tertiles of the TyG index. With an increase in the TyG index, the CACS significantly increased (Spearman’s rho = 0.414, p < 0.001). Poisson regression analysis indicated that the TyG index was independently related to the presence of CAC (prevalence ratio, 1.281 [95% confidence interval, 1.121–1.465], p < 0.001). Furthermore, ROC curve analysis showed that the TyG index was of value in predicting the CAC in asymptomatic non-diabetic patients undergoing MHD, with an area under the curve of 0.667 ( p = 0.010). Conclusion The TyG index is independently related to the presence of CAC in asymptomatic, non-diabetic patients undergoing MHD.