A series of multi-component layered double hydroxides with hydrotalcite structure containing doubly charged magnesium and cobalt cations and triply charged aluminum and iron cations in the brucite-like layers have been synthesized by co-precipitation at variable pH. Formation of the hydrotalcite structure has been confirmed by X-ray diffraction analysis. Thermal behavior of the synthesized samples has been studied by IR spectroscopy, thermogravimetry, and differential thermal analysis.