The chlorination of N-alkoxy-N-alkylureas (1) by the action of t-BuOCl proceeds regiospecifically to give stable N-chloro-N-alkoxy-N'-alkylureas (2). The alcoholysis of 2 leads to N,N-dialkoxy-N'-alkylureas (3). The alkaline hydrolysis of 3 is a new, convenient method for the preparation of dialkoxyamines.