The structure of a range of systematically synthesized polyamides, as well as some corresponding component molecular fragments, were studied using wide angle X-ray scattering and computer modeling methods. The molecules all contained tetra-substituted biphenyls within the amide components, while the aliphatic acid components contained different lengths of the alkyl sequence. A model representing the molecular packing in fiber samples is proposed. It indicates that the polymer backbones are organized in a distorted hexagonal lattice while the intervening pendant side groups still remain randomly packed.