The possible molecule conformation of a new type of polymer surfactant at air/solid interface, acrylamide-poly(oxyethylene alkyl ether)acrylate-anionic monomer random copolymers, was studied by X-ray photoelectron spectroscopy in detail. By means of changing the detection angle, group composition at surface layer in thickness of 0 similar to 2.5 nm can be obtained. The results show that the surface activity of the copolymers related closely with the conformation of the groups of the copolymers. The hydrophobic backbone of the copolymer plays the most important role in enhancing surface activity.