Excellent electrocatalytic properties and low cost are main requirements for the suitable counter electrodes of dye sensitized solar cells (DSSCs). In this work, serials of electrocatalytic films were facilely fabricated by blending the PEDOT polymers and transition metal phosphides nanoparticles (Ni2P or Co2P). All yielded films as counter electrodes were assembled into intact cells and their electrocatalytic performances were carefully investigated. Compared to the PEDOT-only electrode or phosphide-only electrode, the achieved composite electrodes display the superior electrocatalytic performances. The continuous PEDOT polymers can significantly alleviate phosphides nanoparticles aggregations and thereby generate more active area for redox couple. DSSCs with the optimal PEDOT-Ni2P-3 electrode and PEDOT-Co2P-3 electrode show the power conversion efficiency (PCE) of 7.14% and PCE of 6.85%, respectively. And PCE value of the optimal PEDOT-Ni2P-3 is comparable to that (7.09%) of Pt electrode on the same test condition. Moreover, electrochemical measurements reveal the type of composite electrode holding decent dissolution-resistant ability. Considering the outstanding and available electrocatalytic activities, the potential application of PEDOT-phosphides electrodes as the substitute of Pt electrode is worth to be expected.