We developed a new deposition method for perfluoropolyether (PFPE) lubricant on a diamond-like carbon (DLC) overcoat by photoelectron-assisted chemical vapor deposition (PACVD). PFPE lubricant in the vapor phase was deposited on the DLC surface of a magnetic disk with a bias voltage between the disk surface and a counter electrode above the disk surface during ultraviolet irradiation. The bias voltage accelerated the photoelectron emission from DLC surface, and the photoelectrons partially dissociated the PFPE molecules in the vapor phase. The dissociated molecules then chemically bonded to the DLC surface. The PFPE molecules completely chemically bonded to the DLC surface and showed an approximately 100% bond ratio. This produced an ultrathin PFPE/DLC hybrid overcoat as a monolithic film. This hybrid film showed a much lower surface energy than Z-tetraol lubricant film and a high water contact angle of over 100°. This hybrid film increases the head-media clearance and improves some read/write characteristics of the actual heads.