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Background Acute coronary syndrome (ACS) is the leading cause of death in developing and developed countries, yet assessing the risk of its development remains challenging. Several lines of evidence indicate that small, dense low‐density lipoproteins (sd‐LDL) are associated with increased cardiovascular disease risk. We aim to evaluate sd‐LDL concentration for predicting the risk of ACS in Chinese population. Methods Baseline characteristics of 121 patients with ACS and 172 healthy controls were obtained. Plasma sd‐LDL‐C was measured using homogeneous assay, and the proportion of sd‐LDL‐C in LDL‐C was detected. Results There was gender and age effect on the sd‐LDL‐C concentration and sd‐LDL‐C/LDL‐C ratio among healthy subjects. Elevated sd‐LDL‐C concentrations and sd‐LDL‐C/LDL‐C ratio were observed in ACS patients with unstable angina pectoris (UAP), non–ST‐segment elevation myocardial infarction (STEMI), and ST‐segment elevation myocardial infarction (NSTEMI) compared with healthy controls (P < .05); however, there were no differences among ACS groups. According to Pearson's correlation coefficient analyses, sd‐LDL‐C concentration and sd‐LDL‐C/LDL‐C ratio were positively correlated with triglyceride (TG) and LDL‐C concentrations (P < .05) and negatively correlated with high‐density lipoprotein (HDL) concentration (P < .05). Based on the receiver operating characteristic (ROC) curves, the cutoff values of sd‐LDL‐C and sd‐LDL‐C/LDL‐C ratio for the prediction of ACS were 1.06 mmol/L and 34.55%, respectively. Multivariate logistic regression analysis demonstrated that the sd‐LDL‐C/LDL‐C ratio, but not sd‐LDL‐C concentration, was significantly associated with ACS events [OR (95% CI): 1.24, 1.11‐1.38, P < .001]. Conclusions The sd‐LDL‐C/LDL‐C ratio may be associated with an increased risk of developing ACS in Chinese population.