Suitable post-synthesis surface modification of lead-chalcogenide quantum dots (QDs) is crucial to enable their integration in photovoltaic devices. We have developed a solution-phase ligand exchange strategy that exploits arenethiolate anions to replace the pristine oleate ligands on PbS QDs, while preserving the long-term colloidal stability of QDs and allowing their solution-based processability into photoconductive thin-films. Complete QD surface modification is demonstrated by IR spectroscopy analysis, whereas UV-Vis-NIR Absorption Spectroscopy provides quantitative evaluation of stoichiometry and thermodynamic stability of the resulting system. Arenethiolate ligands permit to reduce the inter-particle distance in PbS QD solids, leading to a drastic improvement of the photoinduced charge transport properties. Therefore, smooth dense-packed thin-films of arenethiolate-capped PbS QDs obtained via a single solution-processing step are integrated in heterojunction solar cells: such devices generate remarkable photocurrent densities (14 mA cm(-2)) and overall efficiencies (1.85%), which are outstanding for a single PbS QD layer. Solution-phase surface modification of QDs thus represents an effective intermediate step towards low-cost processing for all-inorganic and hybrid organic/inorganic QD-based photovoltaics.