The arc ion plating (AIP) technique is known to be capable of providing high film deposition rate and strong film adhesion. Titanium dioxide (TiO2) is characterized by its high chemical stability, photocatalysis and biocompatibility nature. The present study employed AIP to deposit TiO2 onto polyetheretherketone (PEEK) at low temperature. This study investigates the microstructure, mechanical and electrochemical properties of the TiO2 coatings as affected by the coating variables for some possible applications. The experimental results indicate that a crystallinic columnar film containing a controllable ratio of anatase to rutile phase can be prepared. The pencil hardness of the PEEK material graded as 4H was increased to over 9H by AIP-TiO2 coating. The film adhesion of the AIP-TiO2 coating can ultimately reach a critical load of 15 N and is associated with its deposition condition, but exhibits the cohesive failure mode (of the scratch scar) regardless of its deposition condition. The polarization behavior of the TiO2 coating in 3.5 wt.% NaCl electrolyte reveals that the AIP-TiO2 coating presents a greater electrochemical inertness if the rutile phase exists. The coating is, however, close to the electrochemical behavior of graphite material in all cases.