A series of piano-stool Ru (II) complexes (Ru1-7) bearing ethylenediamine with aryl and aliphatic groups were prepared and fully characterized by H-1, C-13, F-19 and P-31 NMR spectroscopy, FT-IR and elemental analysis. The crystal structures of Ru2-4 and Ru-7 were determined by X-ray crystallography. They were successfully applied to the alpha(alpha)-alkylation of aliphatic and aromatic ketones with alcohols via the borrowing hydrogen strategy in mild reaction conditions within a short time. The catalytic system has a broad substrate scope, which allows the synthesis of alpha alkylated ketones with excellent yields. The electronic and steric effects of complexes on catalytic activity were analysed. The influence of the carbon chain length of the ligand on the alpha-alkylation reaction of ketones was also investigated. The catalytic cycle was also examined by H-1-NMR spectroscopy in d(8)-toluene.