A series of cruciform aryl‐substituted quinoxalinophenanthrophenazine derivatives (QPPs) was synthesized through Suzuki‐Miyaura cross‐coupling of a 2,7‐diborylated pyrene tetraketal building block. The QPPs were analyzed for their optoelectronic properties by absorption and emission spectroscopy, cyclic voltammetry and quantum‐chemical calculations. The solid‐state packing was investigated as well and evaluated for its charge transport properties by calculated charge transfer integrals.