Ab initio quantum chemical and experimental spectroscopic studies in the infrared (4000-60 cm(-1)) and UV spectral regions are being reported on 4-chloro-2,6-dimethylsulfanyl pyrimidine-5-carbonitrile and 4-chloro-2-methylsulfanyl-6-(2-thienyl) pyrimidine-5-carbonitrile. Optimized geometries, electronic charge distribution, dipole moments and three-dimensional molecular electrostatic potential surfaces have been obtained. These have been used to understand the structure and spectral characteristics of the two compounds. A complete assignment of vibrational spectra on the basis of DFT/6-311G** and electronic spectra on the basis of TD-DFT/6-31+G* 5D calculations have been attempted for the two molecules.