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Nanoceria is an exceptionally versatile, commercially valuable catalytic material whose properties vary dramatically from that of the bulk material.

Amongst various futuristic renewable energy sources, hydrogen fuel is deemed to be clean and sustainable. Electrochemical water splitting (EWS) is an advanced technology to produce pure hydrogen in a cost‐efficient manner. The electrocatalytic hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are the vital steps of EWS and have been at the forefront of research over the past decades. The low‐cost nanostructured metal phosphide (MP)‐based electrocatalysts exhibit unconventional physicochemical properties and offer very high turnover frequency (TOF), low over potential, high mass activity with improved efficiency, and long‐term stability. Therefore, they are deemed to be potential electrocatalysts to meet practical challenges for supporting the future hydrogen economy. This review discusses the recent research progress in nanostructured MP‐based catalysts with an emphasis given on in‐depth understanding of catalytic activity and innovative synthetic strategies for MP‐based catalysts through combined experimental (in situ/operando techniques) and theoretical investigations. Finally, the challenges, critical issues, and future outlook in the field of MP‐based catalysts for water electrolysis are addressed.