Understanding the relationship between molecular/macromolecular architecture and organic thin film transistor (TFT) performance is essential for realizing next-generation high-performance organic electronics. In this regard, planar pi-conjugated, electron-neutral (i.e., neither highly electron-rich nor highly electron-deficient) building blocks represent a major goal for polymeric semiconductors, however their realization presents synthetic challenges. Here we report that an easily accessible (minimal synthetic steps), electron-neutral thienyl-vinylene (TVT)-based building block having weak intramolecular S center dot center dot center dot O "conformational locks" affords a new class of stable, structurally planar, solution-processable, high-mobility, molecular, and macromolecular semiconductors. The attraction of merging the weak TVT electron richness with supramolecular planarization is evident in the DFT-computed electronic structures, favorable MO energetics, X-ray diffraction-derived molecular structures, experimental lattice coehesion metrics, and excellent TFT performance. TVT-based polymer TFTs exhibit stable carrier mobilities in air as high as 0.5 and 0.05 cm(2)/V.s (n- and p-type, respectively). All-TVT polymer-based complementary inverter circuitry exhibiting high voltage gains (similar to 50) and ring oscillator circuitry with high f(osc)(similar to 1.25 kHz) is readily fabricated from these materials by simple inkjet printing.