A novel strategy for fabrication of visible light driven AgBr-alpha-NiMoO4 composite photocatalyst has been developed, including microwave hydrothermal and precipitation-deposition method. The fabrication of heterojunction photocatalyst was proved by XRD, FESEM mapping, HRTEM, SAED, EDS, and XPS techniques. The composite photocatalyst degraded naproxen drug around 84% within 20 min under visible light irradiation. The active species trapping experiment confirmed that OH center dot, O-2(center dot-), and h(+) play a crucial role for naproxen degradation. Due to efficient charge separation, well matched energy band of AgBr and alpha-NiMoO4 as well as surface plasmon resonance of silver particles, the composite revealed the high photocatalytic performance with excellent stability up to fifth cycle. In addition, the composite is photochemical stable. Furthermore, the five degradation pathways were proposed on the basis of retention time and theoretical/observed molecular masses of 19 degraded organic fragments that was confirmed by high-performance liquid chromatography-photodiode array (HPLC-PDA) and high resolution-quadruple time of flight electrospray ionization mass spectroscopy (HR-QTOF ESI/MS) techniques. The different reactions (methylation, demethylation, decarboxylation, hydroxylation, oxidation, and coupling) were observed during NPX degradation by photocatalyst. TOC (total organic carbon) analysis revealed that naproxen drug was completely mineralized by composite photocatalyst within 100 min. So, this work represents the fabrication of visible light induced novel composite photocatalyst for rapid degradation of pharmaceutical pollutant with detailed mechanism and pathways.