The engineering of quantum dot solids with low defect concentrations and efficient carrier transport through a ligand strategy is crucial to achieve efficient quantum dot (QD) optoelectronic devices. Here, we study the consequences of various surface ligand treatments on the light emission properties of PbS quantum dot films using 1,3-benzenedithiol (1,3-BDT), 1,2-ethanedithiol (EDT), mercaptocarboxylic acids (MPA) and ammonium sulfide ((NH4)2S). We first investigate the influence of different ligand treatments on the inter-dot separation, which mainly determines the conductivity of the QD films. Then, through a combination of photoluminescence and transient photoluminescence characterization, we demonstrate that the radiative and non-radiative recombination mechanisms in the quantum dot films depend critically on the length and chemical structure of the surface ligands.