A fluorine-containing methylacrylate copolymer latex has been synthesized by emulsion polymerization and was used as a water- and oil-repellent agent to treat some pure cotton woven fabrics at different dry and curing temperature. The treated cotton fabric surfaces were investigated by attenuated total reflectance infrared analysis and angle-dependent X-ray photoelectron spectroscopy directly. The analysis results could agree with the fluorine-containing copolymer real situation on the fabrics surface much more, and could indicate, factually, surface properties of treated or modified material rather than copolymer film. It was found that fluorine elements are enriched at the air-polymer interface and fluorine content of the treated cotton fabrics surface decreases with increasing analysis depth, which depends on heating and cooling experience, such as annealing and quenching. Furthermore, the results showed that almost the same effect can be attained using this copolymer curing from 100°C to 175°C; the relatively low curing temperature is very valuable and advantageous for some fabrics which would yellow easily at higher temperatures. The water- and oil-repellency grade of treated cotton fabrics by the fluorine-containing methylacrylate copolymer latex increases with an increase on fluorine content on the surface.