A robust in situ nickel oxynitride (Ni x O y N z ) system is synthesized by solid-state annealing of nickel nitride at a relatively low temperature of 400 °C, as confirmed by XRD and Rietveld refinement analysis. XPS investigations revealed that the oxynitride phase is evolved and stabilized by a network involving N 3− , Ni 3+/2+/0 , and O 2− in the system. The enhanced properties of the developed oxynitrides emerged via the synergistic interactions between the nickel nitride−nickel oxide− metallic nickel components, owing to their quantum-cascading electronic band alignments in the system. Consequently, the developed Ni x O y N z system exhibited impressive photocatalytic efficiencies, including ∼98/ 88% degradation of MB/RhB dyes in 150 min and the production of H 2 and NH 3 at rates of 339.7 and 239.8 μmol g −1 h −1 , respectively, under visible light, surpassing the performance of the bare oxide and nitride systems. The improved magnetic properties and photostabilities of the synthesized Ni x O y N z system allowed for easy recovery and reusability, as confirmed in its postcharacterization studies. The findings of the study revealed that the formation of a Ni x O y N z system with tunable phases can be feasible from a pre-engineered Ni 3 N system, and the resulting Ni x O y N z can be a robust photocatalyst for energy-efficient multifaceted photocatalytic applications, as demonstrated in this study.