Energetics and electronic structure of low-lying singlet and triplet valence-excited states of the ortho, meta, and para isomers of thiopyridone were calculated using both density functional theory and multiconfigurational quantum chemistry. Two sets of geometries were optimized in the singlet electronic ground state for each isomer: one, the bare molecule, and the other containing 4 water molecules surrounding the solute. The latter represents a microsolvation cluster, accounting for hydrogen bond coordination with the solute.