In order to improve the tribology behavior in aviation kerosene, molybdenum (Mo) modified layers were fabricated on Ti6Al4V base alloy using a double-glow plasma surface alloying technique. The morphology, microstructure, microhardness and element depth distribution of the Mo modified layers were studied. The tribology properties of Ti6Al4V base alloy, Mo modified layers and 5CrMnMo tool steel sliding with GCr15 steel or QSn4-3 copper alloy counterparts in aviation kerosene were comparatively researched. The effect of roughness on the sliding wear behavior was discussed. The results indicate that the Mo modified layers with polishing treatments not only reduce the friction coefficient of Ti6Al4V base, but also enhance the wear resistance of the counterparts. The Mo modified layers have better tribology behavior than 5CrMnMo steel. It is also found that the wear volume loss of the counterparts is proportional to the value of roughness of Mo modified layers, which is related directly to the ploughing wear between micro convex bodies of the layers and counterparts.