We report the synthesis and characterization of a series of alkoxy-substituted silylethynylated pentacene derivatives (R = CH(2)CH(2), CHCH, CH(2)). All three compounds are easily prepared, soluble in common organic solvents, and stable both as solids and in solution. Two of the derivatives possess significant pi-face interactions in the crystal. Values for lambda(max) for these new pentacene derivatives range from 621 to 674 nm, and oxidation potentials lie between 109 and 301 mV versus ferrocene.