The asymmetric 1,4-addition reaction of arylboronic acids with cycloalkeriones was catalyzed by 1 mol % of an amiclomonophosphine-rhodium(I) catalyst in a 10: 1 mixture of 1,4-dioxane and water at 100 degreesC, affording 3-arylcycloalkanones in reasonably high enantioselectivity and high yields. It was revealed by NMR, IR, and X-ray spectroscopies that this bidentate amidomonophosphine behaves as a hemilabile ligand that contains a hard donor site in addition to the soft donor in a molecule. Phosphorus atom strongly bonds to rhodium(l), and the amide carbonyl oxygen is coordinatively labile. The reaction efficacy of phenylboronic acid with cyclopent-2-en-1-one was significantly dependent on the possibility of coordination of the amide carbonyl oxygen to rhodium(I).