Regioselectivity during the intramolecular reaction of the rhodium carbenoid with a phenyl group tethered by a chiral 2,4-pentanediol is controlled by the steric repulsion and the reaction rate, but when the meta-substituent is a hydroxy group, the regioselectivity becomes unexplainable. Usually, the reaction catalyzed with Rh2(OAc)4 leads the 1,6-addition due to the steric repulsion, but the meta-hydroxy substituted substrate resulted in the 1,2-addition. Use of a Rh2(TFA)4 catalyst resulted in almost no regioselectivity, but the hydroxy group brought 1,6-addition predominantly. These phenomena in the regioselectivity are explainable by the existence of an oxionium ylide intermediate during the addition reactions.