Although phthalates (PAEs) are ubiquitous in drinking water, and phthalate monoesters (MPAEs) have been recognized as the bioactive metabolites of PAEs, little information is available regarding the occurrence of MPAEs in drinking water and the contributions of PAEs and MPAEs to human exposure. In this study, the concentrations of PAEs and MPAEs in 146 samples of drinking water collected from 24 cities throughout China were determined. The mean concentrations of dimethyl phthalate (DMP), diethyl phthalate (DEP), diisobutyl phthalate (DiBP), di-n-butyl phthalate (DnBP), and di-2-ethylhexyl phthalate (DEHP) were 14.31 ± 26.28, 5.905 ± 11.57, 103.8 ± 310.5, 595.9 ± 1794, and 178.2 ± 422.0 ng/L, respectively. Monomethyl phthalate (MMP), monoethyl phthalate (MEP), monoisobutyl phthalate (MiBP), mono-n-butyl phthalate (MnBP), and mono-2-ethylhexyl phthalate (MEHP) were detected in drinking water for the first time, at mean concentrations of 12.1 ± 18.0, 2.4 ± 5.8, 11.3 ± 37.2, 36.3 ± 103, and 9.9 ± 18.0 ng/L, respectively. The geometric mean concentrations of MMP, MEP, MiBP, MnBP, and MEHP in urine samples collected from 1040 participants from 16 cities were 10.1, 19.3, 29.6, 47.3, and 3.63 μg/g creatinine, respectively. The concentrations of PAEs and MPAEs in drinking water and daily intakes (DIs) of PAEs from nine cities where drinking water and urine samples were simultaneously collected were used to estimate the contributions from drinking water. The percentages of DMP, DEP, DiBP, DnBP, and DEHP from drinking water accounted for DIs of 0.60%, 0.049%, 1.26%, 2.76%, and 0.56%, respectively. The percentages of MMP, MEP, MiBP, MnBP and MEHP via intake of drinking water accounted for urinary concentrations of 0.86%, 0.032%, 0.14%, 0.089%, and 0.045%, respectively.