Heteronuclear metal complexes comprising main group metals and transition metals have attracted widespread attention from researchers due to their applications in stoichiometric and catalytic activation of small molecules with possible cooperative effects. Herein, the advances of heterometallic complexes containing Mg- or Zn-metalloligands over the past ten years are reviewed. They consist of two parts: (i) synthetic approaches to heterometallic complexes. Only a brief discussion is made on the different Mg/Zn precursors since they have been summarized before. (ii) Stoichiometric and catalytic reactivities of heterometallic complexes containing Mg/Zn metalloligands. The exploration of the cooperative catalytic reaction of heterometallic complexes is still in its infancy, promising but challenging; thus, further investigations are required in the future.