Charge transport (CT) in films of arylthiolcapped Au nanocrystals (NCs) exhibits strong substituent effects, with electron-donating substituents markedly decreasing conductivity. Films suited for measurements were obtained by ligand-exchange reactions on AuNCs grown at the water/toluene interface. Detailed analysis suggests the NCs interact with the ligands by resonance rather than inductive effects. The films were characterized by TEM, SEM, XPS, UV/vis, and AFM. CT characteristics were studied between 15 and 300 K.