Quantum chemical calculations on the linear and nonlinear electric polarizabilities of dipolar molecules separated by the alkyl spacers have been performed on O2N-Ph-N=N-Ph-(CH2)(n)-Ph-N=N-Ph-NO2, n = 1-12. These molecules exhibit a very strong odd-even behavior in the first hyperpolarizabilities (β), with large (small) β for n = odd (n = even). Such odd-even oscillations have been reported experimentally on similar systems, but the origin of such phenomena remains unclear. We propose it to be due to the role of the conformational orientation of the intervening alkyl spacers that leads to eclipsed orientation (parallel) of the dipoles for n = odd chains while staggered orientation (antiparallel) for n = even chains. The energy difference between the two extreme angular forms is ≈ 6-8 kcal/mol, clearly more than the thermal fluctuations at room temperature. These conformational orientations will be preserved, leading to different packing arrangements at the macroscopic scale. We believe that it is this interaction at the molecular scale that controls such a macromolecular property.