Three-dimensional core-shell organic-inorganic hybrid solar cells with tunable properties are demonstrated via electropolymerization. Air-stable poly(3,4-ethylenedioxythiophene) (PEDOT) shells with controlled thicknesses are rapidly coated onto periodic GaAs nanopillar arrays conformally, preserving the vertical 3D structure. The properties of the organic layer can be readily tuned in situ, allowing for (1) the lowering of the highest occupied molecular orbital level (vertical bar Delta E vertical bar similar to 0.28 eV), leading to the increase of open-circuit voltage (V-OC), and (2) an improvement in PEDOT conductivity that results in enhanced short-circuit current densities (J(SC)). The incorporation of various anionic dopants in the polymer during the coating process also enables the tailoring of the polymer/semiconductor interface transport properties. Systematic tuning of the device properties results in a J(SC) of 13.6 mA cm(-2), V-OC of 0.63 V, peak external quantum efficiency of 58.5%, leading to a power conversion efficiencies of 4.11%.