This study reports on the deposition of a hydrophobic coating on natural leather through a plasma polymerization method and investigates the hydrophobic behavior of the plasma coated substrate. The silicon compound of hexamethyldisiloxane (HMDSO), inactive gas argon (Ar) and toluene were used to impart surface hydrophobicity to a natural leather substrate. Surface hydrophobicity was analyzed by water contact angle, absorption time, and surface free energy measurements. The water contact angle and absorption time results showed that the surface hydrophobicity of natural leather sample was clearly improved after plasma polymerization of HMDSO on the material surface. XPS analysis showed that plasma polymerization of HMDSO/toluene compositions led to a significant increase in atomic percentage of Si compound responsible for hydrophobic surface. These atomic ratios showed that the highest amount of Si and lowest amount of N were obtained with 100 % HMDSO plasma process, confirming the higher degree of plasma polymerization than the other plasma processes. A decrease was observed in total surface free energies of the natural leather samples after plasma deposition indicating improvement in surface hydrophobicity.