The newly developed Z-Scheme Ni3V2O8/AgI visible light photocatalytic heterojunction composite system was fabricated using wet chemical technique with different weight percentages 10, 20, and 30% of Ni3V2O8 for the destruction of (RhB) Rhodamine-B. The purely isolated photocatalyst was further investigated through XRD, UV-vis DRS, TEM, FT-IR, PL, SEM, HRTEM, EDS, and photocurrent measurements. The Ni3V2O8/AgI nanocomposite degraded 82% of RhB with a higher reaction rate coefficient value of 0.0603 min–1 than the other synthesized photocatalysts. The results showed that Z-Scheme heterojunction formation has improved the partition and migration of charged particles leading to intensification in photocatalytic activity when compared to individual photocatalysts. The optimized 20% of Ni3V2O8 nanocomposite was reused three times without any change in photocatalytic performance, which confirmed the stability of the optimized nanocomposite photocatalyst Ni3V2O8/AgI. The outcomes of the radical trapping experiments suggested that radicals •OH and O2•− play a part in RhB degradation. Based on this, a visible light photocatalytic heterogeneous Z-Scheme mechanism is proposed. As a result, the newly fabricated Z-Scheme heterojunction Ni3V2O8/AgI photocatalyst could be a robust material for treating RhB water.