We report the synthesis and photophysical characterization of π‐expanded quinoidal triplet chromophores which exhibit attractive light‐harvesting properties. The kinetic of the triplet excited state of quinoidal benzotetraphene 2 was found to be one order of magnitude higher than the lifetime of 3(1)* from the less conjugated parent chromophore 1. Furthermore, the evaluation of the optoelectronic properties indicates that π‐expansion helps narrow the optoelectronic band gap, but the influence of the additional aromatic rings in the structure of 2 and 3 compromises the stability of the p‐quinoidal ring. QDM 2 was isolated and fully characterized; however, it was found to rearomatize to a mixture of uncharacterized radical species.