The development of new heterogeneous catalysts for Knoevenagel condensation reaction is critical for practical applications. Herein, we prepared three organophosphonate-functionalized polyoxomolybdates, Cs2Na9H9[{Co(H2O)(4)}(TeMo6O21)(2){Co(OOCCH2NCH2PO3)(2)}(3)]center dot 41H(2)O (1), Cs2Na8[H-6{Co(H2O)(4)}(3)(SeMo6O21)(2){Co(OOCCH2NCH2PO3)(2)}(3)]center dot 31H(2)O (2) and Cs2Na9H3[H-6{Ni(H2O)(4)}(SeMo6O21)(2){Ni(OOCCH2NCH2PO3)(2)}(3)]center dot 28H(2)O (3), which exhibit high catalytic activity for gram-scale Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate. Especially, under the optimal conditions, compound 1 can achieve a satisfactory yield (98%) and show high TON value (1960), which is superior to that of compounds 2 and 3. Notably, the TON value is much higher than that of previously reported catalysts. Such high catalytic performance could be attributed to the co-existence of Lewis acid and Lewis base sites in catalysts. In addition, based on substrates screening and recyclability tests, 1 has exhibited broad catalytic generality and good recyclability. [GRAPHICS] .