Continuous studies on the use of a polycyclic aromatic hydrocarbon as the central block of an organic photosensitizer have brought forth a new opportunity toward efficiency enhancement of dye‐sensitized solar cells (DSCs). In this paper, a nonacyclic aromatic hydrocarbon 9,19‐dihydrodinaphtho[3,2,1‐de:3′,2′,1′‐op]pentacene, tethered with four 4‐hexylphenyl solubilizing groups is reported. The novel chromophore 9,9‐19‐19‐tetrakis(4‐hexylphenyl)‐9,19‐dihydrodinaphtho[3,2,1‐de:3′,2′,1′‐op]pentacene is further functionalized with diarylamines and 4‐(7‐ethynylbenzo[c][1,2,5]thiadiazol‐4‐yl)benzoic acid to produce two donor–acceptor (D–A) organic photosensitizers, achieving good power conversion efficiencies up to 10.2% in DSCs.