The microwave hydrothermal and photo-reduction/deposition methods were employed to synthesize silver nanoparticles (Ag NPs) decorated alpha-Nickel molybdate (alpha-NiMoO4) nanorods. TEM image clearly shows the decoration of Ag NPs on alpha-NiMoO4 nanorods. The Ag NPs decorated alpha-NiMoO4 revealed eight folds increase in photocatalytic degradation of tetracycline (TC) compared to the alpha-NiMoO4 under visible light irradiation. The photocatalyst shows excellent stability even after 5th cycle of TC degradation as confirmed by XRD, XPS, and FESEM measurements. In addition, the photocatalyst shows anti-photo corrosion properties. TOC analysis and fluorescence spectroscopy analysis indicate the efficient degradation and mineralization of TC. The enhanced photocatalytic activities of photocatalyst could be attributed to increase in visible light absorption, SPR effect, and efficient separation of electron-hole pairs. The suppression of charge recombination confirmed by PL spectra, transient photocurrent response, EIS, and CV. ESR measurement and scavenger experiment suggest that OH center dot plays a major role whereas O-2(center dot-) and h(+) show the minor role for TC degradation. In order to find out the transformation products in water and degradation pathways of TC, UPLC-PDA and HR-QTOF ESI/MS techniques were used. The five degradation pathways are designed for TC on the basis of demethylation, hydroxylation, dehydroxylation, oxidation, and deamination organic reactions. Moreover, the ESR measurement was used to prove the photocatalytic mechanism. So, this work could provide a fabrication of efficient photocatalyst for removal of pharmaceuticals pollutants from waste water as well as deeper insight into photocatalytic mechanism, transformation products, and degradation pathways of TC in water.