An approach for deriving the bond electro-optical parameters (EOPs) of the bond polarizability model (BPM) from quantum-chemical calculations is proposed. The approach was used to obtain the equilibrium and valence EOPs for the CH and CC bonds in saturated hydrocarbons from the results of the DFT calculations of small chain alkanes. The parameters derived are in the range of those found in the literature. The results of the study show that for this class of molecules the polarizability tensor can be constructed as the sum of the individual bond polarizability tensors thus indicating the validity of the BPM. The use of the parameters in the calculation of the Raman activity of the normal modes of 2-methylbutane shows a good correlation between the data obtained in the DFT calculations and those with the BPM. Factors influencing the reliability and transferability of the parameters are discussed. Copyright © 2006 John Wiley & Sons, Ltd.