The unique benefits of nickel-aluminium layered double hydroxide (Ni-Al LDH)-based heterojunctions, including large surface area, tunable bandgap and morphology, abundant reaction sites, and high activity, selectivity, and photostability, make them extremely promising for photocatalytic applications. Given the importance and benefits of Ni-Al LDH-based heterojunctions in photocatalysis, it is necessary to provide a summary of Ni-Al LDH-based heterojunctions for photocatalytic applications. Hence, in this review, we thoroughly described the material design for Ni-Al LDH-based heterojunctions, along with their recent developments in various photocatalytic applications, i.e., H2 evolution, CO2 reduction, and pollutant removal. Moreover, the most recent advancements, difficulties, and future prospects of Ni-Al LDH-based heterojunctions for photocatalytic applications were emphasized and thoroughly examined. Undoubtedly, in the near future, scientific researchers will put relentless efforts to exploit new Ni-Al LDH-based heterojunctions for high-performance photocatalytic applications.