The synthesis of a series of polymers and cyclopolymers bearing crown ethers of differing structure and affinities towards primary ammonium ions is discussed. These polymers have been tested in their efficiency to form structurally homogeneous thin films when blended with an amphiphilic C-60 compound containing a primary ammonium ion functional group. The X-ray reflectivity characterization of the films revealed that the polymer bearing the crown ether with the least affinity for primary ammonium ions, but having the highest degree of polymerization, is the most effective in forming structurally homogeneous thin films.