In this study, graphitic carbon nitride (g-C3N4, labelled as gCN) was tested in the formulation of copper-free (Cu-free) friction mixtures, which are potentially interesting for brake pad manufacturing. Three formulations of friction composites were prepared starting from a common Cu-free master batch: (i) without graphite, (ii) with graphite and (iii) with gCN. The mixtures were pressed in the form of pins by hot-press moulding. The friction-wear performance of the prepared pins was investigated using a pin-on-disc (PoD) test at room temperature (RT), high temperature (HT) (400 °C) and, again, at room temperature (H-RT). The values of the friction coefficient (µ) for the composites with gCN (or graphite) were as follows: (i) RT test, µRT = 0.52 (0.47); (ii) HT test, µHT = 0.37 (0.37); (iii) RT after the HT tests, µH-RT = 0.49 (0.39). With respect to wear resistance, the samples with graphite performed better than the samples without this solid lubricant. To the best of our knowledge, this is the first report regarding the evaluation of the role of gCN in friction composites designed for automotive brake lining applications. The results indicate the main role of gCN as a soft abrasive.