Three new derivatives containing thieno[3,2-b]thiophene, ethyl 5-(anthracen-9-yl)thieno[3,2-b]thiophene-2-carboxylate 1aethyl 5-(4-yanophenyl)thieno[3,2-b]thiophene-2-carboxylate 1b) and 3-(5-(anthracen-9-yl)thieno[3,2-b]thiophen-2-yl)pyridine (2awere synthesized by arylation reaction in presence of1.0 mol% of Pd(OAc)2. Their structures were elucidated with NMR, MS and XRay analysis. The selectivity of arylation was at C6 of either ester or pyridinesubstituted instead of C2 positions.