A novel DMF-free perovskite solar cell fabrication protocol, based on electrodeposited PbI2 films from ionic liquid and subsequent conversion into perovskite is presented. Hexane is proposed to be used as an efficient co-solvent in the conversion solution, to affect the film morphology in a controlled way. The effect of the hexane in the [CH3NH3-PbI2] (solvent) complex formation and the impact of the complexes in the PbI2 to CH3NH3PbI3 conversion is discussed. Close-packing density nanocrystalline perovskite films from open-packed PbI2 films platelets are successfully obtained after dipping during 10 minutes in isopropanol: hexane 90:10 v:v conversion solutions. Solar cells based on the obtained perovskite films exhibit a power conversion efficiency of 9%. This finding points out the viability of the reported process in the DMF-free fabrication of perovskite solar cells. (C) 2017 Elsevier Ltd. All rights reserved.