In the present study, the catalytic degradation of selected toxic dyes (methylene blue, 4-nitrophenol, 4-nitroaniline, and congo red) using biosynthesized green silver nanoparticles (AgNPs) of Cestrum nocturnum L. was successfully performed. These AgNPs are efficiently synthesized when a reaction mixture containing 5 mL of aqueous extract (3%) and 100 mL of silver nitrate (1 mM) is exposed under sunlight for 5 min. The synthesis of AgNPs was confirmed based on the change in the color of the reaction mixture from pale yellow to dark brown, with maximum absorbance at 455 nm. Obtained NPs were characterized by different techniques, i.e., FTIR, XRD, HR-TEM, HR-SEM, SAED, XRD, EDX, AFM, and DLS. Green synthesized AgNPs were nearly mono-dispersed, smooth, spherical, and crystalline in nature. The average size of the maximum number of AgNPs was 77.28 ± 2.801 nm. The reduction of dyes using a good reducing agent (NaBH4) was tested. A fast catalytic degradation of dyes took place within a short period of time when AgNPs were added in the reaction mixture in the presence of NaBH4. As a final recommendation, Cestrum nocturnum aqueous leaf extract-mediated AgNPs could be effectively implemented for environmental rehabilitation because of their exceptional performance. This can be utilized in the treatment of industrial wastewater through the breakdown of hazardous dyes.