The spreading behavior and multilayer formation of partially fluorinated alternating copolymers are studied. The copolymers are based on substituted N-phenylmaleimides which lack standard hydrophilic groups as well as aliphatic hydrophobic chains. The stability of such vinyl copolymers against thermal degradation is exceptionally high, as are their glass transition temperatures. Despite their unconventional structure, the copolymers form stable monolayers with high collapse pressures. The surface potential of monolayers can be adjusted between positive and negative potentials by well-placed fluorinated substituents. Also, multilayers can be built up by the Langmuir-Blodgett technique.