A doubly interpenetrated metal-organic framework, [Zn-3(TATB)(2)(H2O)(2)](n) (2), with chiral (10,3)-a topology, has been synthesized from an achiral, trigonal-planar ligand, 4,4',4 ''-s-triazine-2,4,6-triyltribenzoate (TATB). The large chiral channels in 2 act as scaffolds for the inclusion of N,N-dimethylaniline (DMA) molecules by donor-acceptor interactions. The resulting host-guest composite, DMA@2, shows desirably intense luminescence, which originated from photoinduced charge-transfer interactions in excited states.