Fabrication of nano size poly(3,4-ethylenedioxythiophene)/multiwalled carbonnanotubes film on a glassy carbon electrode (PEDOT/MWCNT/GCE) in the presence of anionic and cationic surfactants is reported. The modified composite electrodes were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) studies. SEM studies confirmed the formation of nano size film on the working electrode. Electroanalytical studies were carried out using the above prepared electrode by cyclic voltammetry (CV) and differential pulse stripping voltammetry (DPSV). This electrode exhibited higher sensitivity towards the reduction of cypermethrin (CYP), deltamethrin (DEL), fenvalerate (FEN) falling under pyrethroids family and an organochlorine pesticide dicofol (DCF). In CV, all the selected pesticides were found to exhibit one well-defined irreversible reduction peak at pH 13. Optimum conditions for DPSV were experimentally determined by varying several parameters. The practical application of the newly developed sensor was affirmed by quantification of the selected pesticides in spiked water samples.