Two novel dendrimers, 16T and 20T, based on 1,1,2,2-tetra(thiophen-2-yl)ethene (4T) as a new dendron, were efficiently synthesized via carbonylation, Suzuki, and McMurry reactions. All intermediates and title compounds were fully characterized by (1)H NMR, (13)C NMR, and HRMS. 4T and 16T were confirmed by X-ray single crystal analyses. In addition, the absorption behaviors of two titled dendrimers are also described.