The present study investigated the distribution and environmental fate of Bisphenol A (BPA), the 4‐hydroxyacetophenone (4‐HAP) metabolite, and 5 other bisphenol congeners in 2 municipal wastewater treatment plants (WWTPs) and their receiving rivers in Romania. Accordingly, a new, highly sensitive and accurate solid‐phase extraction–liquid chromatography–electrospray ionization–tandem mass spectrometry method was developed and validated. This technique generated low limit of quantitation values: below 2.3 ng/L for surface water and less than 2.4 and 2.7 ng/L for WWTP effluent and influent water. The sum of detected analytes in wastewater was between 1337 and 16 118 ng/L for influent samples and between 15 and 96 ng/L for effluent samples. In surface water, the total of all compounds was somewhere between 34 and 240 ng/L. The highest concentration observed was for BPA in all 3 types of analyzed water (up to 9140 ng/L for influent, as high as 75 ng/L for effluent, and a maximum of 135 ng/L in surface waters). All analyzed samples were free of bisphenols B, C, and F. For all analytes detected in surface water, the concentration values were higher than those determined in the effluent samples, which may be caused by intrinsic contamination of the 2 rivers (Danube and Jiu Rivers). Values of environmental risk coefficients, calculated for both effluents and surface waters, indicated a low ecological risk or no ecological risk for 3 types of organisms (algae, daphnia, and fish). Human risk assessment calculation suggests no risk to human health as a result of the presence of BPA in either of the 2 rivers. Environ Toxicol Chem 2021;40:435–446. © 2020 SETAC