A wide series of 10 new triphenylamine (TPA)/4,4'-dimethoxytriphenylamine (TPA(OMe)2)-functionalized thieno[3,2-b]thiophene (TT) fluorophores, 4a-e and 5a-e, bearing different electron-donating and electron-withdrawing substituents (-PhCN, -PhF, -PhOMe, -Ph, and -C6H13) at the terminal thienothiophene units were designed and synthesized by the Suzuki coupling reaction. Their optical and electrochemical properties were investigated by experimental and computational studies. Solid-state fluorescent quantum yields were recorded to be from 20 to 69%, and the maximum solution-state quantum efficiency reached 97%. Moreover, the photophysical characterization of the novel chromophores demonstrated a significant Stokes shift, reaching 179 nm with a bathochromic shift. They exhibited tuning color emission from orange to dark blue in solution and showed fluorescence lifetime reaching 4.70 ns. The relationship between triphenylamine (TPA)/4,4'-dimethoxytriphenylamine (TPA(OMe)2)-derived triarylamines and different functional groups on thieno[3,2-b] thiophene units was discussed.