Plasma-based ion implantation (PBII) of carbon (time 1-3 h) and subsequent glow discharge deposition of carbon produced TiC/DLC multilayers on Ti-6Al-4V samples (TiC second phase formed in the near surface region plus DLC surface layers). The as-modified samples showed higher hardness than the uncoated sample especially at low plastic penetrations in the order of the 1, 2, and 3 h carbon implantation, but had brittle wear appearances. When the implantation time was increased, the brittleness increased, hence the tribological properties in most cases deteriorated. A tribofilm transferred from a disk wear surface was formed on the wear surface of a counterbody made of bearing steel AISI 52100, lowering the friction coefficient, and reducing the ball wear. When the wear load was decreased and sliding speed increased, the function of the tribofilm became more important; the friction decreased, and the wear properties improved, with a stable friction coefficient ranging from 0.1 to 0.2. But when the counterbody AISI 52100 was changed to Ti-6Al-4V modified as the disk, the tribological behavior surprisingly deteriorated, with wear changing from only disk to both disk and ball abrasive dominated, and it is probably the transferred disk wear debris that caused wear weight increases of the counterbody Ti-6Al-4V.