Hybrid Langmuir and Langmuir-Blodgett monolayers of a perfluorooctadecanoic acid mixed with a rigid block copolymer, poly(3,5-bis(3,5-bis(benzyloxy)benzyloxy)benzyl methacrylate-randommethacrylic acid)-block-poly(2-perfluorooctylethyl acrylate), which is composed of benzyloxy dendron side chains and perfluorinated side chains, were prepared and characterized by surface pressure-surface area isotherms, atomic force microscopic images and neutron and X-ray reflectometries. The two-dimensionally phase-separated structures of monolayer films and their morphologies with plateau and terrace were confirmed. The monolayers were separated into a dendron layer, a perfluorinated layer, and a carboxyl layer. The layer formation is originated not only in the intermolecular interaction between a perfluorooctadecanoic acid and a block copolymer but also in the geometry of the molecules. Especially, the amphiphilicity of perfluorinated surfactant plays a role to the ordered array of the block copolymers.