Water electrolysis for hydrogen production has long been regarded as an ideal tactic for renewable energy conversion and storage, but is impeded by the sluggish kinetics of both the hydrogen and oxygen evolution reactions, which are therefore in urgent need for high-performance but low-cost electrocatalysts. Herein, nanoframes of transition metal phosphides (TMPs) with the 3D framework carved open have been demonstrated as highly potent bifunctional catalysts for overall water splitting, reaching the benchmark performance of the Pt/C‖RuO2 couple, and are much superior to their nanocubic counterparts. This excellent water splitting behavior can be attributed to the enlarged active surface area, less obstructed electrolyte infiltration, promoted charge transfer, and facilitated gas release. Further through in-depth activity analysis and post-electrocatalysis characterization, special attention has been paid to the fate and role of phosphorus in the electrocatalytic process, suggesting that despite the chemical instability of the TMPs (especially under OER conditions), excellent electrocatalytic stability can still be achieved through the amorphous bimetallic hydroxides/oxides formed in situ.