Effects of self-coiling of organic molecules on intramolecular exciplex formation of compound I, in which the carbazole chromophore and terephthalic acid methylester acceptor group are linked by one (CH2)10 chain, and the decrease of the fluorescence intensities of compounds H, Ⅲ, and Ⅳ, in which the carbazole chromophore and 3,5-dinitrobenzoate are connected by one aliphatic chain of (CH2)10 (Ⅱ), (CH2)12 (Ⅲ),or (CH2)4 (Ⅳ), have been studied in the dioxane(DX)-H2Obinary system. The results show that self-coiling of organic molecules in DX-H2O facilitates intramolecular exciplex formation of Ⅰ and induces the decrease of fluorescence intensities of Ⅱ, because of the proximity effect brought about by selfcoiling of organic molecules under hydrophobic-lipophilic interaction (HLI) between the excited carbazole chromophore and the acceptor. Since the similar effects are observed even when the concentrations of the probes are less than their CAgCs (critical aggregate concentratons) in the DX-H2Omixture withthe same φ values, formation of the intermolecular exciplex has been excluded. The effects are found to be strongly depended on φ values, indicating that they are mainly driven by HLI. The properties of the acceptors can also affect the intrmolecular exciplex formation. With terephthalic acid methylester moiety as the acceptor, the carbazole chromophore exihibits the fluorescence spectra of the exciplex,while with 3,5- dinitrobenzoate moiety as the acceptor, only the fluorescence spectra of excited carbazolyl chromphore are observed.