Two examples of heterometallic–organic frameworks (HMOFs) composed of dicarboxyl-functionalized Fe^III-salen complexes and d¹⁰ metals (Zn, Cd), [Zn₂(Fe-L)₂(μ₂-O)(H₂O)₂]⋅4 DMF⋅4 H₂O (1) and [Cd₂(Fe-L)₂(μ₂-O)(H₂O)₂]⋅2 DMF ⋅H₂O (2) (H₄L=1,2-cyclohexanediamino-N,N′-bis(3-methyl-5-carboxysalicylidene), have been synthesized and structurally characterized. In 1 and 2, each square-pyramidal Fe^III atom is embedded in the [N₂O₂] pocket of an L⁴⁻ anion, and these units are further bridged by a μ₂-O anion to give an (Fe-L)₂(μ₂-O) dimer. The two carboxylate groups of each L⁴⁻ anion bridge Zn^II or Cd^II atoms to afford a 3D porous HMOF. The gas sorption and magnetic properties of 1 and 2 have been studied. Remarkably, 1 and 2 show activity for the photocatalytic degradation of 2-chlorophenol (2-CP) under visible-light irradiation, which, to the best of our knowledge, is the first time that this has been observed for Fe^III-salen-based HMOFs.