Highly oriented pyrolytic graphite (HOPG) samples were irradiated by highly charged ions Ar 11+ and Xe 26+. Scanning electron microscopy (SEM), electron spin resonance (ESR), a superconducting quantum interference device (SQUID), and Raman spectroscopy were used to investigate the effect of this irradiation. SEM observations revealed that the contrast between irradiated and unirradiated regions became discernible at a fluence of about 10 14 cm −2. On the other hand, for samples irradiated by Ar + ions, a fluence of the order of 10 15 cm −2 was necessary to obtain a similar contrast to that obtained by Ar 11+ ion irradiation. This demonstrates that highly charged ions effectively enhance modification of solid surfaces. Furthermore, the ESR and SQUID measurements revealed the formation of defects and magnetization of the irradiated surface. Raman measurements were also performed to investigate the structural transformation at different fluences.