This work focuses on the preparation and application of silver nanoparticles/organophilic clay/polyethylene glycol for the catalytic reduction of the contaminants methylene blue (MB) and 4-nitrophenol (4-NP) in a simple and binary system. Algerian clay was subjected to a series of treatments including acid treatment, ion exchange with the surfactant hexadecyltrimethylammonium bromide (HTABr), immobilization of polyethylene glycol polymer, and finally dispersion of AgNPs. The molecular weight of polyethylene glycol was varied (100, 200, and 4000) to study its effect on the stabilization of silver nanoparticles (AgNPs) and the catalytic activity of the resulting samples. The results showed that the catalyst with the highest molecular weight of polyethylene glycol had the highest AgNP content. Catalyst mass, NaBH4 concentration, and type of catalyst were shown to have a significant influence on the conversion and rate constant. The material with the highest silver nanoparticle content was identified as the optimal catalyst for the reduction of both pollutants. The measured rate constants for the reduction of methylene blue (MB) and 4-nitrophenol (4-NP) were 164 × 10−4 s−1 and 25 × 10−4 s−1, respectively. The reduction of MB and 4-NP in the binary system showed high selectivity for MB dye, with rate constants of 64 × 10−4 s−1 and 9 × 10−4 s−1 for MB and 4-NP, respectively. The reuse of the best catalyst via MB dye reduction for four cycles showed good results without loss of performance.