We investigate the introduction of bulky aryl substituents of the biphenyl, terphenyl, and quaterphenyl type at the 6,13 and 5,7,12,14 positions of the pentacene scaffold by reaction of the corresponding quinones with lithium organic reagents. The 1,1′‐biphenyl‐2‐yl substituent could be installed at the 5,7,12,14‐positions and regioselectively either at 6,13 or at the 5,13 positions. The unsymmetrical substitution motif results from concomitant 1,2 and 1,4‐addition to 6,13‐pentacenequinone. A one‐pot protocol leads to isomeric symmetric 6,13‐disubstituted pentacenes and allows installation of two 5′‐phenyl‐[1,1′:3′,1′′‐terphenyl]‐2‐yl substituents. The four new pentacenes differ in crystal packing and photochemical stability. [ABSTRACT FROM AUTHOR]