Silicon (Si)/organic polymer hybrid solar cells have great potential for becoming cost-effective and efficient energy-harvesting devices. We report herein on the effects of polymer coverage and the rear electrode on the device performance of Si/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hybrid solar cells with micro-pyramidal structures. These hybrid solar cells provided adequate generation of charge carriers owing to the suppression of reflectance to below 13%. Additionally, the separation of the photogenerated charge carriers at the micro-pyramidal-structured Si/PEDOT:PSS interface regions and their collection at the electrodes were dramatically improved by tuning the adhesion areas of the PEDOT:PSS layer and the rear electrode materials, thereby attaining a power conversion efficiency of 8.25%. These findings suggest that it is important to control the PEDOT:PSS coverage and to optimize the rear electrode materials in order to achieve highly efficient separation of the charge carriers and their effective collection in micro-textured hybrid solar cells.