The effects of two cationic chemical modified β-cyclodextrins, quaternary ammonium β-CD and tertiary amine β-CD on fluorescence systems, such as Zr(IV)-Morin, Zr(IV)-Quercetin, Al(III)-Ferron, and Al(III)-H2QS, were studied comparatively with β-CD. A mechanistic investigation has been conducted using pyrene as probe molecule for the media polarity changes in its surrounding microenvironment. The different effects of various CDs or CD-surfactant mixtures on these systems have been interpreted in terms of formation and geometric compatibility of multicomponent complexes, fluorescence quantum yield ratio of fluorophoric complex to that of the corresponding fluorophoric reagent. The chemical structure of fluorophoric reagent was also considered. Some characters of ionized chemical modified β-CDs were deduced. The mechanism of the synergistic fluorescence enhancement of β-CDs with surfactant was discussed preliminarily.