The taming of the shrew! For the first time, a broadly applicable efficient room-temperature Arbuzov rearrangement is described. This reaction is accomplished through an atom-economical Lewis acid catalyzed process (see scheme, TMSOTf=trimethylsilyl trifluoromethanesulfonate). The method has been generalized to primary and activated secondary phosphites, phosphinites, and phosphonites. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2003/z50270_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.