High reflectivity is essential when a metal is used as back contact and reflector in thin-film silicon solar cells. We show that thermal annealing at 150 °C improves the reflectivity of silver films deposited by sputtering at room temperature on nanotextured substrates. The annealing provokes two interlinked effects: rearrangement of the silver layer with a modification of its morphology and an increase of up to 42% in the grain size of the polycrystalline film for the preferential orientation as measured by X-ray diffraction. The main consequence of these two mechanisms is a large increase in the reflectivity of silver when measured in air. This reflectivity increase is also noticeable in devices: amorphous silicon thin-film solar cells grown on annealed silver films yield higher internal and external quantum efficiencies compared to cells grown on as-deposited silver. The morphology modification smoothes down the substrate, which is revealed by a clear increase of the open-circuit voltage and fill factor of the cells grown on top. An amorphous silicon cell with a 200 nm nominally thick i-layer fabricated on a flexible plastic substrate yielded an initial efficiency close to 10% with 15.9 mA/cmof short-circuit current using highly reflective annealed textured silver. We also propose, for industrial purpose, the sputtering of thin silver layer (120 nm) under moderate substrate temperature (∼150 °C) to increase the layer reflectivity, which avoids lengthening of the back reflector fabrication.