We report ab initio molecular dynamics calculations based on density functional theory performed on an intramolecular [2 + 2] cycloaddition between ketene and olefin linked with a 2,4-pentanediol (PD) tether. We find that the encounter of the ketene and olefin moieties could be prearranged in the thermal equilibrated state before the cycloaddition. The reaction mechanism is found to be stepwise, similar to that of intermolecular ketene [2 + 2] cycloadditions with ordinary alkenes. A distinct feature of the reaction pathway for a major diastereoisomer is a differential activation free energy of about 1.5 kcal/mol, including 2.8 kcal/mol as the differential activation entropy, with a transition state consisting of a flexible nine-membered ring in the olefin-PD-ketene moiety. This theoretical study provides a reasonable explanation for the strict stereocontrollability of the PD-tethered ketene-olefin cycloaddition, irrespective of reaction types or conditions.