Composites of Laponite and Cu–Mn hopcalite-related mixed oxides, prepared from hydrotalcite-like (Htlc) precursors obtained in inverse microemulsions, were synthesized and characterized with XRF, XRD, SEM, TEM, H₂ temperature-programmed reduction (TPR), and N₂ adsorption/desorption at −196 °C. The Htlc precursors were precipitated either with NaOH or tetrabutylammonium hydroxide (TBAOH). Al was used as an element facilitating Htlc structure formation, and Ce and/or Zr were added as promoters. The composites calcined at 600 °C are mesoporous structures with similar textural characteristics. The copper–manganite spinel phases formed from the TBAOH-precipitated precursors are less crystalline and more susceptible to reduction than the counterparts obtained from the precursors synthesized with NaOH. The Cu–Mn-based composites are active in the combustion of toluene, and their performance improves further upon the addition of promoters in the following order: Ce < Zr < Zr + Ce. The composites whose active phases are prepared with TBAOH are more active than their counterparts obtained with the use of the precursors precipitated with NaOH, due to the better reducibility of the less crystalline mixed oxide active phase.