Five phosphotungstate-incorporated metal-organic frameworks {[Eu-4(dpdo)(9)(H2O)(16)PW12O40]}(PW12O40)(2 center dot)(dpdo)(3)center dot Cl-3 (1); {ZnNa2(mu-OH)(dpdo)(4)(H2O)(4)[PW12O40]}center dot 3H(2)O (2); {Zn-3(dpdo)(7)}[PW12O40](2)center dot 3H(2)O (3); and [Ln(2)H(mu-O)(2)(dpdo)(4)(H2O)(2)][PW12O40]center dot 3H(2)O (Ln = Ho for 4 and Yb for 5) (dpdo = 4,4'-bipyridine-N,N'-dioxide) have been synthesized through a one-step hydrothermal reaction and characterized by elemental analyses, infrared (IR) spectroscopy, photoluminescence, and single-crystal X-ray diffraction (XRD). The structural analyses indicate that 1-5 display diversity structure from one-dimensional (ID) to three-dimensional (3D) series of hybrids. Kinetic experiments for the hydrolytic cleavage of DNA-model phosphodiester BNPP (bis(p-nitrophenyl)phosphate) were followed spectrophotometrically for the absorbance increase at 400 nm in EPPS (4-(2-hydroxyethyl)piperazine-1-propane sulfonic acid) buffer solution, because of the formation of p-nitrophenoxide with 1-5 under conditions of pH 4.0 and 50 degrees C. Ultraviolet (UV) spectroscopy indicate that the cleavage of the phosphodiester bond proceeds with the pseudo-first-order rate constant in the range of 10(-7)-10(-6) s(-1), giving an inorganic phosphate and p-nitrophenol as the final products of hydrolysis. The results demonstrate that 1-5 have good catalytic activity and reusability for hydrolytic cleavage of BNPP.