The fluorescence behavior of a calixarene with a dansyl group as fluorescence marker (C6-DA) was investigated with respect to the inclusion properties of alkaloids as atropine and cocaine. A strong hypsochromic shift of the fluorescence band and a strong increase in fluorescence intensity is connected with the interaction of atropine to the lower rim of the C6-DA. The fluorescence increase is saturated at an atropine concentration above the 1:1 complex formation. Addition of cocaine to the complexed atropine-C6-DA leads to a decrease of the fluorescence intensity which could be explained by an exchange mechanism of the complexed molecules. The complexation of the atropine (the “belladonna effect”) is interpreted by electrostatic interaction (proton transfer from the carboxylic group to the nitrogen) with important contribution from hydrogen bonding by the guest OH-group.