A method for depositing silver nanoparticles in a pre-patterned trench by site-selective synthesis is described. In the trench patterns with various shapes, silver nanoparticles can be selectively nucleated and grown only on polyvinylpyrrolidone (PVP) domains by attraction (or repulsion) between silver ions and the hydrophilic PVP island domains in a silica matrix of the trench (or the hydrophobic fluorosilane layer). Regarding the silver nanoparticles in the trench, localized surface plasmon resonance (LSPR) could be excited by obliquely incident light, reradiating the enhanced electromagnetic field in the far- and near-fields. Even in the case of a large angle incidence in total internal reflection (TIR), the patterned silver nanoparticle clusters underwent strong scattering with a high intensity, due to the LSPR effect.