Depositing an ultra-thin tetrahedral amorphous carbon (ta-C) protective coating on the surface of the recording heads in magnetic tape drives can improve the tribological problems at the head/tape interface. In this work the effect of pre-treatment of the surface of AlTiC substrate (main bearing surface of head in contact with tape) by C⁺ ions of moderate energy (smaller than 400 eV) on the structural and tribo-mechanical behaviours of the coated surfaces is studied. Sample preparation consisted of two separate stages of surface pre-treatment and deposition of the protective film, and was done by means of filtered cathodic vacuum arc. Structure of the ta-C film and its interface with the substrate were studied by transmission electron microscopy and time-of-flight secondary ion mass spectrometry depth profiling. The results revealed the formation of a broader, dense atomically mixed layer at the ta-C film–substrate interface of the pre-treated samples comparing with that of the samples without pre-treatment. Chemical characterization of thin diamond-like carbon coatings was conducted by means of x-ray photoelectron spectroscopy and the surface pre-treatment was found to have a remarkable effect on increasing the sp³ hybridization fraction in the ta-C overcoat. Nano-tribological properties of the treated surfaces were examined using ball-on-flat wear test at very low load (20 mN). There was a good correlation between the surface and structure characteristics of the film, and the tribological results and the pre-treated surfaces presented a very low coefficient of friction and higher wear life. The experimental results demonstrate the effectiveness of bombardment of the surface with C⁺ ions of moderate ion energy to improve the structural and tribo-mechanical properties of the protective ta-C films on the magnetic head substrate material.