A new method has been developed to prep. [(Ph₃P)₃Ru(CO)(H)₂] (1), an important homogeneous catalyst, directly from RuCl₃·xH₂O. Unlike previously reported procedures to make 1, the new method does not utilize toxic and hazardous materials such as formaldehyde and benzene and requires only a small excess of PPh3, while furnishing anal. and spectroscopically pure 1 in unprecedented >95% yield. The solvent (EtOH) is used in small quantities, thereby enabling scalability, as has been demonstrated by prepg. >17 g of pure 1 in one batch..