Electrocatalytic activity of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) modified glassy carbon electrode is explored for Pu(IV)/Pu(III) redox couple in 1 M H2SO4 and its performance is compared with conventionally used electrodes (Au, Pt and GC). The morphology of modified electrode is seen by scanning electron microscopy and its composition is verified by energy dispersive spectroscopy. Cyclic voltammetry and differential pulse voltammetry shows enhanced electrocatalytic activity of modified electrode as it shows maximum current density, least peak potential separation and higher electron transfer rate constant for Pu(IV)/Pu(III) couple as compared to Au, Pt and GC electrode. Electrochemical impedance spectroscopy also confirms our experimental results as the modified electrode shows least charge transfer resistance as compared to conventional electrodes. Trace quantity of Pu detection is possible in a short interval of time with higher sensitivity by differential pulse voltammetry technique that shows the modified electrode can be used for Pu determination in nuclear fuels. (C) 2016 Elsevier Ltd. All rights reserved.