The behavior of supramolecular polymers in solution is well understood, but their utilization in organic electronics is centered around solid-state thin films. Thin films are crucial components of organic transistors, light-emitting diodes, solar cells, lasers, and sensors. Specifically chiral, π-conjugated moieties have received recent attention due to their ability to exhibit macroscopic chiral self-assembly, leverage the Chirality Induced Spin Selectivity (CISS) effect, and show circularly polarized luminescence. This unique property gives rise to catalytic spin-filtration in electrochemical processes such as green hydrogen production and opens the gates for novel spintronic devices. The supramolecular assembly of these molecules is key to optimizing current enhancement, spin-filtration, and photosensitization at electrochemical interfaces. The scope of this work covers the synthesis of benzodithiophene (BDT) derivatives and the characterization of biphenyl dithiophene (BPDT) derivatives both in solution and in thin films. BDT and BPDT were selected for their excellent charge transport properties, C2 molecular symmetry, broad visible absorption bands, and versatility as either N-type or P-type materials depending on functionalization. Two BDT derivatives with varying acceptor and donor positions were synthesized as candidate materials for thin film preparation via chemical vapor deposition, spin coating, and drop casting. The effect of film preparation methodology and molecular functionality on solid-state supramolecular assembly was probed using three BPDT derivatives. Blue shifts in absorbance maxima of BPDT thin films provided an initial indication of supramolecular aggregation. Electronic Circular Dichroism (ECD) spectroscopy further showed chiral self-assembly in spin-coated thin films of urethane-functionalized BPDT and donor-acceptor-donor BDT. These fundamental studies show promise for the eventual roles of these molecules in electrode coatings and optoelectronic thin films. Film uniformity and supramolecular order could be further improved in vapor-deposited films. Still, the extensive use of the technique requires optimization of material utilization, especially for extensive use with high-value molecules.