A novel pillared-layered entangled luminescent metal-organic framework [Zn2(bpdc)2(BPyTPE)] (1) (BPyTPE = (E)-1,2-diphenyl-1,2-bis(4-(pyridin-4-yl)phenyl)ethene) has been designed and constructed. The solvent-free 1 exhibits strong blue-green emission with an excellent fluorescence quantum yield of 99% and provides a facile and reversible method to sensitively and quantitatively detect trace pesticide of 2,6-dichloro-4-nitroaniline.