The invention discloses a method for simultaneously measuring residues of 12 kinds of OPEs (Organophosphate Esters) in a water sample and sediment, belongs to the technical field of measurement of organophosphorus esters, and discloses a method for detecting residues of 12 kinds of phosphate ester compounds in a water body and sediment by using a high-performance liquid chromatography-mass spectrometry technology in combination with solid-phase extraction and liquid-liquid extraction. The method comprises the following steps: enriching a water sample with an HLB (Hydrophile-Lipophile Balance) solid-phase extraction column; extracting sediment with an ultrasonic solvent; analyzing by a high-performance liquid chromatography-mass spectrometer MRM (Multiple Reaction Monitoring) monitoring ion mode; quantifying by an external standard method. Specific to most OPEs, the method has the advantages of low detection limit, high stability and high detection sensitivity; when the method is used for rapidly screening the OPEs in the water body and the sediment, the detection requirement on the residues of 12 kinds of OPEs in the water body and the sediment can be met basically.