The present paper reports the detailed computational study of a series of Polyene TTF analogues 1-4 within DFT method and B3LYP/6-31G (d,p) basis set. The calculated HOMO and LUMO energies show that charge transfer within the molecules. Stability of the molecules arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital analysis (NBO). The dipole moment (µ), polarizability (Δα) and first order hyperpolarizability (β) of the molecules were calculated. Molecular electrostatic potential (MEP) and Fukui functions were also performed.