Organic thin film transistors (OTFTs) have attracted intensive attention for potential applications in flexible displays, low-cost electronic papers. In recent years, my group has developed facile [X+1+Y] one-pot synthetic routes for DTT (dithienothiophene), BTDT (benzothienodithiophene), TTA (tetrathienoacene), and PTA (pentathienothiophene) preparation. A few new fused-thiophene-based derivatives have been developed for OTFTs. For example, we reported stable soluble BTDT-based materials with 0.65 cm2V-1s-1 mobility fabricated via a solution process. For recent p-type materials development, we have developed two new soluble small molecules which exhibit mobilities of 1.7 and 2.6 cm2V-1s-1, fabricated via a solution process. The later will be the Taiwan highest mobility small molecules via a solution process. For n-type materials development, we have developed a few new air-stable quinoidal molecules, for example, DTTQ exhibits ~0.45 cm2V-1s-1 mobility in air (AFM). Notably, these newly developed thiophene-based units are good building blocks and can be applied in OPV, 2PA, DSSC, and PSC. For example, our TTA-based small molecules and thioalkylated thiophene-based polymers have exhibited 4% and 9.4% PCE in OPV, respectively. Our newly developed TTA-based chromophores exhibited high 2PA properties, up to 3000 GM, which is the highest performance of fused-thiophene-based 2PA chromophores. Our new developed TTA-based organic dyes exhibited PCE up to 11.2%, which set a new record in Taiwan. Lastly, our new developed hole transporting layer (HTL) small molecules in Sn-based PSC (perovskite solar cell) exhibited 7.23%, which is one of the best HTLs in the world.Here in this project, we will continue preparing our newly-developed high-performance materials for their devices optimization and then published these good results. At the same time, new thiophene-based molecules will be explored for OTFT, OPV, DSSC, 2PA, and PSC. The optical/electronic performance of these new materials will be evaluated.