Abstract <p>Efficient synthetic methods have been developed for hybrid compounds based on layered yttrium hydroxide (LYH) intercalated with malonate complexes of <i>d</i>-metals (Cr³⁺, Fe³⁺, Ni²⁺, Cu²⁺, or Zn²⁺) and <i>f</i>‑metals (Eu³⁺ or Tb³⁺). The influence of the anion-exchange reaction temperature and the nature of the intercalated metal cations on the orientation and coordination modes of malonate anions in the LYH interlayer space has been systematically studied. The amount of incorporated <i>d</i>- and <i>f</i>-metal cations increases in the following order: Tb³⁺ &lt; Ni²⁺ &lt; Zn²⁺ &lt; Cu²⁺ &lt; Cr³⁺ &lt; Eu³⁺ &lt; Fe³⁺. These findings demonstrate that malonate-intercalated LYH is a versatile platform for the design of novel <i>d</i>- and <i>f</i>-metal-based hybrid materials.</p>