An elegant method (modified sol-gel method) was developed to fabricate porous silver (Ag) monoliths using Tween-85 (T-85) as a reducing agent with and without dextran (Dex) and TiO 2 nanoparticles (TiO 2 NPs) for heterogeneous catalysis for the reduction of methyl orange (MO) using sodium borohydride (NaBH 4 ), as reducing agent and also sensor against caffeine. Ag/Tween-85/Dextran/TiO 2 NPs (Ag/T-85/Dex/TiO 2 NPs) catalyst was characterized by thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), UV-Vis spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) adsorption isotherm technique, and Fourier transform infrared (FTIR) analysis. Porous Ag/T-85/Dex/TiO 2 NPs monolith degraded toxic dye methyl orange just in 25 seconds (s) which is the minimum time reported. Cyclic voltammetry (CV) using modified carbon paste electrode (CPE) together with Ag/AgCl as reference and pt as counter electrodes with 0.1 m H 2 SO 4 as supporting electrolyte were used. Ag/T-85/Dex/TiO 2 NPs À CPE acts as a sensor against caffeine with a limit of detection (LOD) and limit of quantization (LOQ) 0.654 ng mL À 1 and 0.876 ng mL À 1 respectively and sensitivity is 0.236 μA/mm/cm 2 .