Poly(3,4-ethylenedioxypyrrole) (PEDOP), combined with metal-free organic sensitizers, is efficiently used for the first time as the hole-transporting material in solid-state dye-sensitized solar cells. Devices employing PEDOP as the hole conductor and D35 or D21 L6 as the sensitizer show a ten-times-higher energy-conversion efficiency (of 4.5 % and 3.3 %, respectively) compared to Ru-Z907-based devices. This is due to the efficient suppression of electron recombination. An efficient combination! Poly(3,4-ethylenedioxypyrrole) (PEDOP) is used for the first time as the hole-transporting material in solid-state dye-sensitized solar cells. Devices containing PEDOP as the hole conductor and D35 or D21 L6 as metal-free organic sensitizers show a tenfold higher energy conversion efficiency compared to Ru-Z907-based cells. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.