NiFe-LDH has been recognized as the most efficient and cost-effective material for wider applications in electrocatalytic, photoelectrocatalytic, and photocatalytic water splitting, with supercapacitors and adsorbents, owing to their inimitable physicochemical properties. It is well known that standalone NiFe-LDH executes poor electrical conductivity, sluggish mass transfer, and low activity, which put a question mark on their catalytic efficiency and other applications that require superior electrical conductivity and exciton pair separation efficiency. Most importantly, this constraint creates a hindrance to their superior performance in the area of electrocatalytic and photochemical water splitting. To avoid these shortcomings, the coupled structure of NiFe-LDH/graphene has the potential to reflect properties of both NiFe-LDHs and conductive graphene, which completely overcome the shortcomings of counterparts, ensuring better performance and stability. This review aims to summarize the structural impact of NiFe-LDHs, with the interfacial role of graphene/graphene oxide (GO) by establishing a relationship between their structure and activity. Moreover, the emphasis has been laid on the latest development in NiFe-LDH/GO-based materials, along with attention to synthetic methods targeting the creation of a hierarchal porous nature in the materials with different growth approaches to NiFe-LDH on graphene for applications in electrocatalytic, photoelectrocatalytic, and photocatalytic water splitting activities. The latest research and development in this field using NiFe-LDH/graphene with a sensible intermixing of active sites and conductive framework is explored.