Rear surface morphology and multilayer silver embedded in molybdenum oxides as hole-selective layers (HSLs) were proposed to enhance the photovoltaic characteristics of screen-printed monocrystalline silicon solar cells (SPMSCs). Moreover, the charge trapping characteristic of multilayer silver embedded in molybdenum oxides was presented. The results suggested an improvement in the conversion efficiency of more than 1.0% absolute from 17.7% to 18.7% for SPMSCs with a flat rear surface and three layers of Ag embedded in MoOx as HSLs were demonstrated. The mechanism was attributed to an increase in a negative fixed charge and high rear reflection.