Oxygen-containing organic compounds, such as ethers, carboxylates, and carbamates, have recently received increasing attention because of their newly discovered applications as electrophiles in cross-coupling reactions via transition metal-catalyzed C-O bond activation. However, no cycloaddition reaction involving their C-O bond activation has been demonstrated thus far. The present study developed a Ni(O)-catalyzed unique [3+2] cycloaddition reaction of alpha,beta-unsaturated phenyl esters with alkynes in (i)PrOH to yield cydopentenone derivatives.