The N-[3-(trimethoxysilyl)propyl]ethylenediamine (EDAS) derived silicate matrix supported core-shell TiO(2)-Au nanoparticles (EDAS/(TiO(2)-Au)(nps)) were prepared by NaBH(4) reduction of HAuCl(4) precursor on preformed TiO(2) nanoparticles in the presence of EDAS monomer. The core-shell (TiO(2)-Au)(nps) nanoparticles were stabilized by the amine functional group of the EDAS silicate sol-gel network. The potential application of this EDAS/(TiO(2)-Au)(nps) modified electrode toward the photoelectrochemical oxidation of methanol was explored. The EDAS/(TiO(2)-Au)(nps) modified electrode showed a 12-fold enhancement in the catalytic activity toward photoelectrooxidation of methanol when compared to TiO(2) dispersed in EDAS silicate sol-gel matrix. This improved photoelectrochemical performance is explained on the basis of beneficial promotion of interfacial charge transfer processes of the EDAS/(TiO(2)-Au)(nps) nanocomposite. A methanol oxidation peak current density of 12.3 mA cm(-2) was achieved at an optimum loading of Au(nps) on TiO(2) particles. This novel amine functionalized EDAS silicate sol-gel stabilized core-shell (TiO(2)-Au)(nps) nanomaterial could be an excellent candidate for the photocatalytic and photoelectrochemical applications.