Silver nanoparticles were successfully assembled in self-organized polyhedral TiO2; synthesized by hybrid template consisting of pluronic-85, hexadecyltrimethylammoinm bromide and triethanol amine (TPHtAg(2)), as well as in platelets TiO2; synthesized only via hexadecyltrimethylammonium bromide (THAg2). X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, diffuse reflectance UV-vis spectroscopy as well as N-2 sorptiometry were used for the characterization of phase composition, surface morphology, valent states of Ag/TiO2, optical and surface texturing properties. These nanomaterials were tested as catalysts for 4-nitrophenol (4-NP) reduction in presence of aqueous NaBH4 under visible-light irradiation. The results showed that the THAg2 catalyst exhibited the best photocatalytic performance in the reduction of 4-NP into 4-aminophenol (4-AP) and revealed 98% conversion following 2 min irradiation with rate constant equal 0.025 s(-1). On the other hand, the TPHtAgS(2) catalyst, derived from using Ag2SO4 as a precursor instead of AgNO3, indicates a conversion comprised of 80% at similar reaction conditions. The superiority of the photocatalytic reduction of THAg2 was due to exposing Ag+ ions together with Ag-0 nanoparticles (5 nm) and to the photo-induced role of carbon atoms; formed as a result of the non-complete decomposition of the template, and its synergistic effect with the anatase phase. On the contrary, TPHtAg(2) showed strong chemical interaction of Ag+ ions within the hybrid templates and as a result inhibits the reduction of Ag+ ion as well as the adsorption of 4-NP and eventually indicates no activity. The decreased activity and stability of TPHtAgS(2) compared with THAg2 was due to increasing the particles size of Ag-0 (10 nm), diminishing the accessibility and reactivity of Ag+ ions; which could have been worked as trapping sites with Ag-0, and the limited effect of residual S2- ions, depicted from XPS measurements. (c) 2013 Elsevier B.V. All rights reserved.