Organophosphate esters (OPEs), as flame retardants and plasticizers, have been numerously explored regarding the occurrence and ecotoxicology. Given their toxicity, persistency and bio-accumulative potential, however, they may pose negative effects on ecosystems, regarding which is a growing global concern. Accordingly, the present review systematically analyses the recent literature to (1) elucidate their worldwide distribution, bioaccumulation, and biomagnification potential, (2) determine their interim water quality criteria (i.e., effect thresholds), and (3) preliminarily assess the ecological risks for 32 OPEs in aquatic ecosystems. The results showed that the spatiotemporal distribution of OPEs was geographically specific and closely related to human activities (i.e., megacities), especially halogenated-OPEs. We also found that precipitation of airborne particulates could affect the concentrations of OPEs in soil, and there was a positive correlation between the bioaccumulation and hydrophobicity of OPEs. Tris(2-ethylhexyl) phosphate may exhibit high bioaccumulation in aquatic organisms. A substantial difference was found among interim water quality criteria for OPEs, partly attributable to the variation of their available toxicity data. Tris(phenyl) phosphate (TPHP) and tris(1,3-dichloroisopropyl) phosphate with the lowest predicted no-effect concentration showed the strongest toxicity of growth and reproduction. Through the application of the risk quotient and joint probability curve, TPHP and tris(chloroethyl) phosphate tended to pose moderate risks, which should receive more attention for risk management. Future research should focus on knowledge gaps in the mechanism of biomagnification, derivation of water quality criteria, and more precise assessment of ecological risks for OPEs.