Phthalic acid esters (PAEs) are well-known ubiquitous environmental pollutants and used as plasticizers for the manufacturing of plastic products. During this exploratory study, an attempt has been made to determine the concentration and distribution of five prominent PAEs, viz. di-methyl phthalate (DMP), di-ethyl phthalate (DEP), di-butyl phthalate (DBP), di-(2-ethylhexyl) phthalate (DEHP), and di-octyl phthalate (DOP) in the sediment samples of Gomti River collected from 30 different locations. Identification and quantification of PAEs were performed by high-performance liquid chromatography. The mean concentration values of DMP, DEP, DBP, DEHP, and DOP were found as 10.54, 4.57, 10.41, 31.61, and 5.16 μg/kg, respectively. Limit of detection and limit of quantification for each PAE were also calculated and found in the ranges of 0.09–0.55 and 0.28–1.67 μg/kg. DEHP was the most frequently detected PAE (present in 93.3% samples); however, DOP was found only in 36.7% samples.