A series of Cu-based mixed oxides were prepared by calcinations of corresponding CuMgAl-layered double hydroxides precursors at different temperatures with nominal Cu/Mg/Al ratios of 1 : 1 : 2(Cu-LDH-1), 1 : 2 : 1(Cu-LDH-2),1 : 1 : 1(Cu-LDH-3), and 2 : 1 : 1(Cu-LDH-4). The synthesized catalysts were characterized using X-ray diffraction, high-resolution transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, inductively coupled plasma atomic emission spectroscopy (ICP-AES), and N2 physisorption analysis techniques. All as-obtained catalysts showed adequate catalytic performance for the alpha-alkylation of ketones with alcohols through a hydrogen autotransfer mechanism. The catalyst CuMgAl-I-650 (obtained by calcining Cu-LDH-1 at 650 degrees C) displayed the highest activity and selectivity. Using this catalyst system, a wide range of branched ketones were synthesized in good to excellent isolated yields. Moreover, the catalyst CuMgAl-I-650 could be recycled and reutilized for four cycles without any significant loss of activity and selectivity. This study provides a very simple and inexpensive catalysis based on transition metals, which are in abundance on earth. A novel Cu-based composite metal oxides catalyst derived from CuMgAl hydrotalcite was prepared and the catalyst exhibits a great catalytic performance for alpha-alkylation of ketones with alcohols. In addition, the catalyst was recycled and reutilized for four cycles without any significant loss of activity and selectivity. Meanwhile, the catalytic system was tolerant of a wide range of substrates. image