<p>The generation of hydrogen through photo/electrocatalytic water splitting is a highly promising strategy for addressing the current energy crisis and environmental challenges, with the ultimate goal of achieving zero carbon emissions. Nowadays, the majority of electro/photocatalysts for the water decomposition process are traditional noble metals and transition-based metal oxides. However, their slow kinetics, small surface area, limited active areas, and cost-effectiveness limit their use. A novel category of porous electro/photocatalysts is metal–organic frameworks (MOFs), which possess intriguing properties such as a large surface area, porosity, low density, and the ability to adjust their activity. MOFs have garnered substantial attention in the field of electro/photocatalytic H₂ and O₂ production recently as a result of their multifunctional nature and specific characteristics. MOF and its derived nanomaterials offer various benefits, including long-term stability, efficient charge separation and transport, and a wide range of light absorption. This critical review describes the modern advancements in MOFs and their derivatives for the electrocatalytic hydrogen evolution reaction (cathode), the oxygen evolution reaction (anode), and the photocatalytic hydrogen and oxygen generation process. Furthermore, we address the critical parameters of the aforementioned process. Lastly, we offer an in-depth review of the current challenges and opportunities in electro/photocatalysis, as well as the potential for the development of next-generation advanced metal organic frameworks to be addressed.</p> Graphical Abstract <p></p>