Synthetic access to new push-pull molecules based on 3-cyano-4-hexyloxythiophene and triphenylamine moieties is presented herein using a clean methodology. The key step involves a direct heteroarylation coupling reaction in the presence of a homogeneous or heterogeneous [Pd] catalyst followed by Knoevenagel condensation performed in ethanol as a solvent. Structure-electronic property relationships of the new molecular materials are discussed and then their use as donors in bilayer planar heterojunction solar cells is investigated.