Two Ni-added poly(polyoxometalate)s built of Keggin-type {Ni6PW9} and Anderson-type NiW6O24 units via WO4/Sb2O bridges and Ni-O-W linkages, Na4H8[Ni(enMe)2][(Sb2O)2(NiW6O24)-{Ni12O2(OH)4(enMe)4(H2O)3(WO4)2(B-α-PW9O34)2}2]·39H2O (1) and H9[Ni(en)2(H2O)][Ni0.5(en)2(H2O)][Ni-(enMe)2(H2O)][(Sb2O)2(NiW6O24){Ni12O2(OH)4(en)2(enMe)2(H2O)3(WO4)2}-{Ni12O2(OH)4(en)4(H2O)3(WO4)2}(B-α-PW9O34)4]·45H2O (2), have been hydrothermally synthesized and characterized, in which the {Ni12(WO4)2(PW9)2} subunit was obtained by the synergistic directing effect of 2 lacunary PW9O34 (PW9) fragments and further linked by a central Anderson-type (Sb2O)2(NiW6O24) bridge. Both compounds represent the first example of Ni-added polyoxometalates (POMs) simultaneously based on Keggin-type and Anderson-type POM components. Photocatalytic studies revealed that 2 can work as an efficient heterogeneous catalyst towards a light-driven H2 evolution reaction, achieving a hydrogen evolution rate of as high as 19 214 μmol g-1 h-1 (TON = 1500), which is superior to most of the reported POM-based heterogeneous catalysts.