Multinuclear Pr-containing antimonotungstate [Pr4(H2O)10W6O13(mal)2(OAc)(B-α-SbW9O33)4]21- (Pr-1, mal = malate anion, OAc = acetate anion), bridged by organic carboxylic acid, was synthesized through a one-pot assembly reaction and structurally characterized. Pr-1 is composed of four [B-α-SbW9O33]9- fragments fused together by an organic-inorganic hybrid central [Pr4(H2O)10W6O13(mal)2(OAc)]15+ cluster core through 24 μ2-O atoms. Notably, the central cluster comprises unprecedented decanuclear Pr4(H2O)10W6O13 jointly decorated by two types of carboxylic acid ligands. This integration of rare earth-containing antimonotungstate with mixed organic carboxylate ligands is very rare in POMs chemistry. Pr-1 exhibits excellent catalytic activity in the cyclo-condensation reaction involving benzil, aldehyde, and NH4OAc. A series of 2,4,5-trisubstituted imidazoles were synthesized in remarkable yields using iPrOH as a green solvent.