A new LC/MS method for the determination of organophosphorus pesticides in water, based on the use of direct-electron ionization (EI) interface, is presented. Direct-EI is a new device that, in a very simple fashion, couples a nano-HPLC system with a mass spectrometer equipped with electron ionization capability. The nanoscale liquid flow allows for a direct introduction of eluate into the ion source and, after nebulization, for its ionization under typical EI conditions. Library-matchable EI spectra are generated for a choice of full scan or SIM detection of the analytes. In our case, a selection of organophosphorus pesticides, commonly distributed in local sugar beet cultivation, were considered. The new interface permits a very sensitive detection of the analytes in a wide range of linear response (0.09-9 ng). When applied to a real sample, the method allowed detecting four different pesticides at a concentration level of approximately 3 ng x L(-1).