Ti–Al–Si–C–N coatings are deposited by hybrid arc-enhanced magnetron sputtering and characterized by various micro and macro-tools. X-ray diffraction, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy reveal that the coatings are probably nanocomposites consisting of nanocrystallites and amorphous phases. They are generally in the form of nc-(Ti,Al)(C,N)/a-SiN/a-C, depending on the composition of the coatings. With increasing Al concentrations, the X-ray diffraction peaks shift to a lower angle and the measured hardness diminishes, implying a reduced contribution of the self-organized stable nanostructure. The dry friction coefficients of the Ti–Al–Si–C–N coatings are about 0.3, which is lower than that of conventional Ti–Si–N coatings. These coatings can find potential applications requiring heavy contact loading subject to high temperature.