A novel wheel-shaped Zr-substituted phosphotungstate, [N(CH 3 ) 4 ] 2 K 16 Na 10.5 H 10.5 [{Zr(C 2 O 4 ) 2 } 3 (PO 4 )(P 6 W 39 O 150 )]⋅45H 2 O was prepared, which exhibited a high proton conductivity of 1.18 × 10 −2 S cm −1 at a higher temperature of 368 K.