Two new Krebs-type tungstoantimonates (H(2)en)(8)H-6{[Sb-2(WO2)(2)(B-beta-SbW9O33)(2)] - [(WO2)(2) (WO3)(2)(B-beta-SbW9O33)(2)]}center dot 22H(2)O (1) and (H(2)en)(7)[(WO2)(2)(WO3)(2)(B-beta-SbW9O33)(2)]center dot 12H(2)O (2) were synthesized and characterized. Notably, crystal 1 possesses a specific pseudo-seesaw SbO4 subunit in the central metal belt of [Sb-2(WO2)(2)(B-beta-SbW9O33)(2)](1)(2-) species, which is rare in reported Krebs-type polyoxometalates. One of the structural features is that there are two kinds of Krebs-type polyanionic clusters in crystal 1 labeled as {(WO2)(2)(WO3)(2)(B-beta-SbW9O33)(2)} (part A) and {Sb-2(WO2)(2)(B-beta-SbW9O33)(2)} (part B), respectively. The subunits A and B are alternately connected through Sb-O-W bonds into a chain-like structure of inorganic clusters. Moreover, the catalytic property of crystals 1 and 2 for electron-transfer reaction were investigated by transferring K-3[Fe(CN)(6)] into K-4 [Fe(CN)(6)].