A method of controlling oxygen purge of a three-way catalyst may include: performing a fuel cut-off; determining whether a fuel cut-in condition is satisfied after the fuel cut-off; calculating an optimum valve overlap according to an intake amount, an engine rotation speed, and an ignition timing if the fuel cut-in condition is satisfied after the fuel cut-off; controlling a CVVD apparatus to be at the optimum valve overlap; and performing the oxygen purge at the optimum valve overlap.