A novel and efficient palladium-catalyzed direct mono and tetraarylation of tetrathienylethene with various arylbromides to synthesize donor-acceptor system of tetrathienylethene-arene (TTE-Ar) luminophores is reported. The mono- and tetra-arylated TTEs shown an emissive phenomenon, including photoluminescence in various organic solvents and aggregation induced emission (AIE) effect because TTE acts both as an electron-donor for intramolecular charge transfer (ICT) and as activator for AIE. The photoluminescence and AIE of these aryl-substituted TTEs are characterized.