Magnesium-aluminum-bismuth layered double hydroxides (Mg3Al1−xBix; LDHs) were prepared using both coprecipitation and sol-gel methods. For the preparation of Mg/Al/Bi LDH by the co-precipitation method, the appropriate amounts of dissolved starting materials (Al(NO3)3 · 9H2O, Mg(NO3)2 · 6H2O and Bi(NO3)3 · 5H2O) were mixed with a solution of NaHCO3:NaOH. In the sol-gel processing, the precursor Mg–Al–Bi–O gels were synthesized using the same starting materials and ethylene glycol as complexing agent. The mixed-metal oxides obtained by subsequent heating of Mg–Al–Bi–O gels at 650 °C were reconstructed to Mg3Al1−xBix LDHs in water at 80 °C. All the synthesized products were characterized by X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM) and dielectric measurements.