This study reports on the deposition of a hydrophobic coating on polyurethane (PU)-based synthetic 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 PU-based substrate. Surface hydrophobicity was analyzed by water contact angle measurements. Surface hydrophobicity was increased by deposition of compositions of 100% HMDSO, 3:1 HMDSO/toluene, and 1:1 HMDSO/toluene. Optimum conditions of 40 W, 30 s plasma treatment resulted in essentially the same initial contact angle results of approximately 100A degrees for all three treatment compositions. The initial water contact angle for untreated material was about 73A degrees. A water droplet took 1800 s to spread out on the plasma-treated sample after it had been placed on the sample surface. An increase in plasma power also led to a decrease in contact angle, which may be attributed to oxidization of HMDSO during plasma deposition. XPS analysis showed that plasma polymerization of HMDSO/toluene compositions led to a significant increase in atomic percentage of Si compound responsible for the hydrophobic surface. The easy clean results for the treated and untreated PU-based synthetic leather samples clearly showed that the remaining stain on the plasma-polymerized sample was less than that of untreated sample. The plasma-formed coating was both hydrophobic and formed a physical barrier against water and stain.