Utilizing a streamlined five-step synthesis process, we have successfully produced a diverse set of adjustable benzo [4,5]thieno-S,S-dioxide-[3,2-b]benzofurans-based compounds through Michael's addition-elimination reaction, Suzuki-Miyaura coupling, and intramolecular oxidative C-H/C-H coupling, in 70-90% yields. The synthetic strategy employed demonstrates that the compounds can be modified on either side by introducing various types of groups at positions 2 and 3, with the possibility of extending the aromatic portion in place of the benzofuran. Thus, these compounds exhibit a distinctive dual-state emission, showcasing very good quantum yields up to 63% in solid state and 83% in solution. Additionally, these compounds have been integrated into ambient condition, solution-processed, non-doped OLEDs, demonstrating promising results with a luminance of 850 cd/m 2 and a turn-on voltage of 3.50 V.