Synthetic organic chemists endeavor to develop new reaction conditions, improve product yields, and enhance atom economy (synthetic methodologies), whereas the material scientists strive to create novel functional molecules/structures, increase device stabilities, and promote power conversion efficiencies via device engineering (organic optoelectronics). However, these two prominent research fields seem to have no intersections. Since joining national central university in 2012, our research philosophy aims to narrow, or rather to bridge the gap between synthetic methodologies and π-functional organic materials. In contrast to using multistep synthetic approaches based on Suzuki- or Stille coupling reactions, this personal account describes various step-saving and viable synthesis-shortcuts developed by our group, to access thiophene-based small molecules for optoelectronic applications. We expect these succinct and user-friendly alternative pathways designed by synthetic chemists would help material scientists to reach their target molecules in a more step-economical manner.