A variety of substituted 2-cyclohexenones, such as (R)-1, is obtained enantiomerically pure by employing the chiral copper–phosphoramidite complex [Cu(OTf)2L*] as a highly efficient catalyst for their kinetic resolution (>99 % ee at 52 % conversion, selectivity S>200). These important building blocks can be obtained on a synthetically interesting scale, as was demonstrated by the successful multigram resolution of 5-methyl-2-cyclohexenone. Tf=trifluoromethanesulfonyl. Supporting information for this article is available on the WWW under http://www.angewandte.com 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.