Two hourglass-type molybdophosphate hybrids with the formulas [Cd(H2O)(2)DABT](4)[Cd(H7P4Mo6O31)(2)].19H(2)O (1) and (C2H5OH)(C3H5N2)(6)[Co-3(H6P4Mo6O31)(2)].H2O (2) (DABT= 3,3'-diamino-5,5'-bis(1H-1,2,4-triazole)) have been successfully designed and synthesized via a hydrothermal method. Structure analysis revealed that the inorganic moieties in compounds 1 and 2 are made up of hourglass-type {M[P4Mo6](2)} (M = Cd/Co) structure, which were constructed by two (P4Mo6) units with single transition metal (TM) (Cd/Co) atom as the central metal. The {M[P4Mo6](2)} (M = Cd/Co) structures were then further connected by TM to constitute a 2D layered structure. Surprisingly, under the condition of 60 degrees C and 98% RH, compounds 1 and 2 exhibited excellent proton conductivity of 1.35 x 10(-3) and 3.78 x 10(-3) S cm(-1), respectively. Furthermore, compound 2 can act as heterogeneous catalyst for CO2 photoreduction, which indicates that it may be a bifunctional POM-based material with great promise.