Here, the optical properties of a series of structurally well-defined model compounds for oxidatively degraded poly(dialkylfluorenes) (PFs) are reported. Specifically, linear compounds comprising one, two, or four dihexylfluorene (F) moieties together with one fluorenone (O) moiety placed either at the end or in the center of each chain (i.e., FO, FFO, FOF, FFOFF) are studied. The results support the recent observation that the photophysics of the fluorenone-centered ''pentamer'' (FFOFF) is most similar to that of oxidized PFs. They further demonstrate that molecule-molecule interaction is essential to activate the green emission band. Investigations by X-ray diffraction (XRD) identify the solid-state structure of a representative member of this class of compounds and reveal inter-molecular interaction through dipole-dipole coupling between neighboring fluorenone moieties. ©2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.