In this work, we report the results of solid state structural study of a series of oligothiophenes and ethylenedioxythiophenes (EDOT) endowed with bromine atoms at different positions and in the presence/absence of the strong electron acceptor, the tricyanovinyl group (TCV). Five new compounds were synthesized, crystallized and their single crystal structures were determined by X-ray diffraction. The impact of bromine atom(s) on solid state packing as viewed through analysis of intermolecular interactions is presented. Comparative study using experimental, computed and published data of closely related structures shows intra-molecular interactions involving Br in the presence of TCV and EDOT. Distances shorter that the summation of the Van der Waals radii were observed which indicate the role of Br…NC, S…S and Br…Br interactions in addition to pi stack formation and planarity of these compounds due to the presence of strong electron acceptors. Possible implications of how these structural features may impact charge transport in oligothiophenes will be discussed.