Background: Phthalates are widely used in consumer products, food packaging, and personal care products, so exposure is widespread. Several studies have investigated the association of phthalate exposure with obesity, insulin resistance, and hypertension. However, little is known about the associations of phthalate exposure with sex, age, and menopausal status in metabolic syndrome (MetS). The purpose of this study was to investigate the association between 11 urinary phthalate metabolite concentrations and metabolic syndrome in adults. Methods: We conducted a cross-sectional analysis of 1337 adults aged 30–70 years from the Taiwan Biobank 2016–2020. Prevalence odds ratios (POR) and 95% confidence intervals (CIs) were calculated using logistic regression and stratified by sex, age, and menopausal status. Results: Participants with MetS comprised 16.38%. Higher concentrations of MEP metabolites were associated with more than two- to three-fold increased odds of MetS in males and males ≥ 50 years (adj. POR Q3 vs. Q1 = 2.13, 95% CI: 1.01, 4.50; p = 0.047 and adj. POR Q2 vs. Q1 = 3.11, 95% CI: 0.13, 8.63; p = 0.029). When assessed by menopausal status, postmenopausal females with higher ∑DEHP concentrations had more than nine-fold higher odds of MetS compared with postmenopausal females with the lowest ∑DEHP concentrations (adj. POR Q3 vs. Q1 = 9.58, 95% CI: 1.18, 77.75; p = 0.034). Conclusions: The findings suggest differential associations between certain phthalate metabolites and MetS by sex, age, and menopausal status.