A detailed mechanism for the Kulinkovich hydroxycyclopropanation reaction has been explored with density functional theory calculations on the reactions between (RCOOMe)-C-1 and Ti(OMe)(2)(CH2CHR2) (R-1 and R-2 are hydrogen and alkyl groups). Addition of ester to titanacyclopropane is found to be fast, exothermic, and irreversible. It has a preference for the alpha -addition manifold over the beta -addition manifold in which its cycloinsertion transition states suffer from the steric repulsion between the R-2 and ester. The following intramolecular methoxy migration step is also exothermic with reasonable activation energy. The cyclopropane forming step is the rate-determining step, which affords the experimentally observed cis-R-1/R-2 diastereoselectivity in the alpha -addition manifold by generating cis-R-1/R-2 1,2-disubstituted cyclopropanol when R-1 is primary alkyl groups. On the contrary, the unfavored beta -addition manifold offers the diastereoselectivity contradicting the experimental observations. The effects of R-1 and R-2 on the regio- and stereoselectivity are also discussed.