We report herein the syntheses of dodecamethoxytricyclobutabenzene (TCBB) 1 and hexaoxo-TCBB 2, a class of molecules with structural and theoretical interest. The preparation is based on the 3-fold [2 + 2] cycloadditions of benzyne and ketene silyl acetals (KSAs), where the selectively protected 2-iodophloroglucinol derivative served as a synthetic equivalent of benztriyne I, allowing rapid and regioselective annulation of fully functionalized four-membered rings. Structural study on the former compound showed that the C-C bond lengths in the central benzene ring were essentially the same.