Commercial dull polyethylene terephthalate (PET) fabric treated by radio frequency (13.56 MHz) plasma and further coated with perfluoroalkyl methacrylate copolymer C6 displays much highly durable hydrophobicity and oleophobicity. The as-prepared fabric exhibited a water contact angle above 170°, a water spray rating of 80 (ISO 3), and oil resistance ratings of B and C separately for different oil composition grades after 10 washing cycles, which were two levels higher than the untreated and C6-coated PET[TiO2] fabric. The organic component PET was more prone to etching than TiO2, which created a waviness structure and exposed prominent TiO2 nanoparticles on the PET fiber surface. The relative atom ratio O and Ti increased through energy-dispersive X-ray spectroscopy spectra and X-ray photoelectron spectroscopy analysis. This result indicates that the exposure of TiO2 and the introduction of reactive polar groups such as O=C-O on the fiber surface contributed to react with C6 and improved the washing durability. In general, such coating technology may provide a simple benign technique for constructing materials with physicochemical properties.