Several types of β-ketoamino based N,O-coordinate halfsandwich ruthenium complexes have been synthesized in moderate to good yields. The stable ruthenium complexes displayed good and diverse catalytic efficiency in reductive amination between aldehydes and amines in aqueous solution. The method gave a facile route for one-pot synthesis of diverse complicated amines with a low catalyst loading by using cheap and less-toxic HCOOH or clean H 2 as hydrogen source. Catalyst Ru1 showed the highest catalytic activity of 190 h −1 TOF value in the reductive amination reaction of benzaldehyde with aniline. The corresponding amine products were furnished in excellent yields under the standard catalysis system. The efficient and diverse catalytic activity, broad substance scope, mild conditions, and environmentally benign solvent made this system potentially applicable in industrial production. Ruthenium complexes were characterized using NMR, elemental analysis, and IR techniques to confirm their structure.