The films of octadecene, dodecene, and undecenoic acid were prepared on H-terminated Si surface in the presence of ultraviolet irradiation. The resulted films were characterized with water-contact angle measurement and infrared spectroscopy. The friction-reducing behavior of the prepared films was examined on a static-dynamic friction coefficient measurement apparatus and on an atomic force microscope. It was found that all the reacted films on the Si substrate showed good friction-reducing ability; especially, the film of the octadecene exhibited the best frictionreducing ability. This was attributed to the transfer of the reacted films onto the counter face with formation of a transfer film on the counterpart surface, which led to the transformation of the sliding between the reacted films and the hard ceramic to that between the reacted films and its transfer film on the counterpart surface. The macroscopic and microscopic friction behaviors of the prepared films were dependent on their molecular chain lengths. Thus the octadecene reacted film with the highest degree of ordering arrangement showed the best friction-reducing and antiwear abilities in sliding against Si3 N4.