Purpose: To investigate low-density lipoprotein cholesterol (LDL-C) goal attainment rates in patients with hypercholesterolemia treated with atorvastatin/ezetimibe or atorvastatin monotherapy. Methods: This was a multicenter, noninterventional, retrospective, chart review study of Korean patients with hypercholesterolemia who were statin-naïve and prescribed atorvastatin/ezetimibe or atorvastatin monotherapy during an observational period, from January 2014 to July 2017, and followed up for 12-18 weeks. Patients were propensity score matched to reduce treatment selection bias. Outcomes included LDL-C goal attainment rate at week 12, defined by risk groups according to Korean Society of Lipidology and Atherosclerosis guidelines; and change in lipid parameters from the index date to week 12. Results: A total of 969 patients were enrolled in the study: atorvastatin/ezetimibe, n = 349; atorvastatin monotherapy, n = 620. Following propensity matching (n = 316 in each group), respective LDL-C goal attainment rates for atorvastatin/ezetimibe and atorvastatin monotherapy groups were 86% and 75%, respectively (p = 0.0004). Atorvastatin/ezetimibe produced significantly larger reductions at week 12 in mean LDL-C (−50.3% vs −42.7%), total cholesterol (−36.8% vs −30.7%) and non-high-density lipoprotein cholesterol (non-HDL-C; −47.3% vs −39.8%) levels compared to atorvastatin monotherapy (all p < 0.0001). Conclusion: More patients achieved LDL-C goal attainment with atorvastatin/ezetimibe than with atorvastatin monotherapy, and atorvastatin/ ezetimibe was associated with significantly larger reductions in mean LDL-C, total cholesterol and non-HDL-C levels than atorvastatin monotherapy, in Korean patients with hypercholesterolemia in a real-world clinical practice.