A novel organotin-substituted polyoxomolybdate cluster (H(3)O)(16)[(H(2)O)(2)Mo(V)O(OH)](2){Mo(VI)(28)Mo(II)(4)(NO)(4)(BuSnO)(2)[BuSn(OH)(2)](2)O(102)(H(2)O)(12)}.18H(2)O was synthesized in a 'one-pot' reaction by adopting the reduction-oxidation-reconstitution self-assembly process, which shows a {Mo(34)(NO)(4)Sn(4)} mixed metal skeleton, which is constructed from two {Mo(16)(NO)(2)Sn(2)} subunits being linked by two MoO(6) octahedra.