A new crystalline microporous organic-inorganic hybrid material containing a chimine fluorophore inside the framework has been synthesized solvothermally without using any template or structure-directing agent (SDA). Powder XRD and N-2 sorption analyses suggested the formation of a new triclinic phase and supermicropores of dimension 1.39-1.53 nm in this material, C-13 CP MAS, Si-29 MAS NMR, UV/Vis absorption and PL spectroscopic results suggested the presence of bridging organic chimine fluorophore in this new porous framework, Due to the use of sole fluorophore organosilane moiety in this organic-inorganic hybrid framework, this material shows very large affinity toward metal cations like Fe3+, Zn2+, Cd2+ and Hg2+, and thus can be efficiently utilized as metal ion chemosensor and exchanger. All the metal ion-exchanged samples show very strong photoluminescence at room temperature and strong dependence of emission colors when exchanged with a particular metal cation. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)