Transition metal phosphides have been known as promising electrocatalysts for hydrogen evolution and oxygen evolution reactions (HER and OER) due to their high catalytic activity. In this work, the FeCoP nanoparticles decorated on N-doped electrospun carbon nanofibers (FeCoP@NCNFs) was successfully synthesized through depositing Fe, Co-based Prussian blue analogue Co3[Fe(CN)6]2·10H2O (FeCo-PBA) onto the electrospun PVP/PAN nanofibers via layer-by-layer approach, followed by carbonization and phosphorization treatments. Benefiting from the high electrical conductivity, abundant catalytic active sites and the synergistic effect between FeCoP nanoparticles and N-doped carbon nanofibers network, the obtained FeCoP@NCNFs displays good bifunctional electrocatalytic activity. In 1 M KOH, the FeCoP@NCNFs achieves 10 mA cm−2 at an overpotential of 290, 226 mV for OER and HER, respectively. Moreover, it demands overpotential of 196 mV to achieve 10 mA cm−2 for HER in 0.5 M H2SO4. The FeCoP@NCNFs is used as both anode and cathode for overall water splitting, it requires a low voltage of 1.65 V to achieve a current density of 10 mA cm−2 and maintains outstanding stability over 10 h. Herein, a strategy for preparing bifunctional electrocatalysts of compositing transition metal phosphides with carbon nanofibers is proposed, and the application of metal-organic framework in electrocatalytic field is further extended.