With the environmental pollution and non-renewable fossil fuels, it is imperative to develop eco-friendly, renewable, and highly efficient electrocatalysts for sustainable energy. Herein, a simple electrospinning process used to synthesis Mo2C-embedded multichannel hollow carbon nanofibers (Mo2C-MCNFs) and followed by the pyrolysis process. As prepared lotus root-like nanoarchitecture could offer rich porosity and facilitate the electrolyte infiltration, the Mo2C-MCNFs delivered favourable catalytic activity for HER and OER. The resultant catalysts exhibit low overpotentials of 114 mV and 320 mV at a current density of 10 mA cm(-2) for HER and OER, respectively. Furthermore, using the Mo2C-MCNFs catalysts as a bifunctional electrode toward overall water splitting, which only needs a small cell voltage of 1.68 V to afford a current density of 10 mA cm(-2) in the home-made alkaline electrolyzer. This interesting work presents a simple and effective strategy to further fabricating tunable nanostructures for energy-related applications.