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We aim to explore the association between caffeine and its metabolites and bone mineral density (BMD) in postmenopausal women. Data of 4286 postmenopausal women were extracted from the National Health and Nutrition Examination Survey (NHANES) database in 2009–14 in this cross-sectional study. Weighted linear regression and stepwise regression analyses were used to screen the covariates. Weighted univariate and multivariate linear regression analyses were used to explore the associations between caffeine and its metabolites and BMD. The evaluation index was estimated value (β) with 95 % confidence intervals (CIs). We also explored these relationships in age subgroups. The median BMD level among the eligible women was 0⋅7 gm/cm2. After adjusting for covariates including age, body mass index (BMI), fat intake, Calcium (Ca) supplements, diabetes mellitus (DM), angina pectoris, parental history of osteoporosis (OP), anti-osteoporosis therapy, poverty income ratio (PIR), vitamin D (VD) supplements, coronary heart disease (CHD), and previous fracture, we found that caffeine intake was not significantly related to the BMD reduction (β = 0, P = 0⋅135). However, caffeine metabolites, including MethyluricAcid3, MethyluricAcid7, MethyluricAcid37, Methylxanthine3, and Methylxanthine37, were negatively associated with the BMD (all P < 0⋅05). In addition, MethyluricAcid37 and Methylxanthine37 were negatively associated with BMD in females aged <65 years old, while MethyluricAcid3 and Methylxanthine3 were noteworthy in those who aged ≥65 years old. The roles of caffeine and its metabolites in BMD reduction and OP in postmenopausal women needed further exploration.