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Crystalline materials containing hybrid inorganic–organic metal borates (complexes with oxidoborate ligands) display a variety of novel framework building blocks. The structural aspects of these hybrid metallaoxidoborates containing Cd^(II), Co^(II), Cu^(II), Ga^(III), In^(III), Mn^(II), Ni^(II) or Zn^(II) metal centers are discussed in this review. The review describes synthetic approaches to these hybrid materials, their physical properties, their spectroscopic properties and their potential applications.