The structures of liquid crystalline disubstituted biphenylcyclohexanes (BCHs) of the general formula R-C6H10-C6H4-C6H4-X with R: C3H7; X: H (BCH30), and R: C5H11; X: CN (BCH5CN) have been optimized using the density function B3LYP with 6-31+G (d) basis set using crystallographic geometry as input. Using the optimized geometry, electronic structures of the molecules have been evaluated using the density functional theory (DFT) calculations. Mulliken atomic charges for each molecule have been compared with Loewdin atomic charges to understand the molecular charge distribution and phase stability. The electronic absorption spectra and circular dichroism (CD) spectra of BCH molecules have been simulated by employing the DFT method. The excited states have been calculated via configuration interaction single level (CIS) with semiempirical Hamiltonian ZINDO. Two types of calculations have been performed for model systems containing single and double molecules of BCHs. Further, the spectra have been reported for all single molecules, and the ultraviolet (UV) stability of the molecules has been discussed. The stacked and in-plane dimer complexes have also been reported to enable the comparison between single and double molecules.