The use of metal sulfides for organic photovoltaics has been a widely studied topic in recent years. The current study reports on the impact of aniline and piperidine ligands on the transport and optical properties of SnS/CoS heterostructure, using the first principles density functional theory approach. The charge transfer properties possess an electropositive and electronegative feature for both the aniline and piperidine ligands, respectively. This charge transfer behaviour is consistent with metal-to-ligand charge transfer properties. The optical properties of SnS/ligand/CoS retain its optical plasmonic transitions for both ligand types, with a corresponding damping effect in the absorption, which suggests interfacial charge transfer-type interactions. Also, an increased density of states for both ligand types is observed, implying increased availability of unoccupied states for electronic transport. These results of ligand-incorporated SnS/CoS suggest its potential for future improved charge transfers in organic solar cells.