The carbazolyldiacetylenes show very different fluorescence behaviors depending on how the carbazolyl (Cz) moiety is connected to the diacetylenic backbone. In fact, when Cz is attached to the backbone through one or more CH2 spacer(s) fluorescence properties are observed which are closely related to those of the fluorescent Cz group. On the contrary, almost no fluorescence is observed when Cz is directly attached to the backbone. In this paper, these phenomena are studied quantum chemically and an explanation for the observed facts is provided. The relevant excited states are studied in detail, showing that in the lowest singlet excited state a considerable intramolecular charge transfer occurs from Cz to the backbone when they are directly bonded.