A detailed study of the different parameters of the higher homologs of the 5O.m (m = 14, 16) series of liquid-crystalline compounds is reported. These are interdigitated compounds with unsymmetrical alkyl chain length. The compounds have a unique nature, unlike the other members of the nO.m series. The molecular structure reported in this article is not purely uniaxial; it has a bending tendency. In this article, we report that both the compounds exhibit negative birefringence. For the optical study, the refractive indices, n(e) and n(o), of the sample are measured by the thin-prism technique, using a He-Ne laser beam of wavelength 633 nm. A four-parameter model was used for fitting the experimental results. From the experimentally measured refractive indices, it is possible to compare different parameters with those of the theoretical models.