alpha-Hydrazinophosphonates (N-hydroxy-alpha-aminophosphonates) are generated by lithium perchlorate-catalyzed three-component reaction of aldehydes, N,N-dimethylhydrazine (phenylhydroxylamine) and trimethylphosphite/trimethylsilyl chloride (acetic acid). The method utilizes cheaply available reagents and hence it is a practical and cost effective strategy, compared to other methods available in the literature.