This report explores the use of sacrificial thin polymer films prepared by surface-initiated polymerization as a template for the fabrication of highly conformal metal nanoparticle solar cell electrodes. As a first proof-of-principle, the use of this method is demonstrated to prepare top electrodes on planar and microwire-based silicon solar cell devices. These metal nanoparticle films are dual functional in that they not only mediate charge transport, but also enhance light capture due to the plasmonic scattering properties of the nanoparticles. Solar cells with a conformal silver nanoparticle-based electrode layer show short circuit currents that are 46% higher as compared to those exhibit by devices coated with standard indium tin oxide as the electrode. It is anticipated that this methodology will contribute to novel electrode concepts in the next generation solar cells.