Polyphilic surfactants made up of a carboxylic hydrophilic headgroup, a biphenyl rigid core, a flexible hydrocarbon spacer, and a perfluorinated chain are used to build Langmuir-Blodgett multilayers. The films are investigated by X-ray reflectivity, infrared dichroism, and scanning electron microscopy. At the transfer pressure used, the molecular area is consistent only with molecular long axes orthogonal to the air-water interface. Such a situation is retained for the first transferred monolayer whose thickness is equal to the molecular length in the fully elongated conformation, For thick films however, molecular long axes are tilted toward the dipping direction. Such a finding involves a rearrangement which does not retain the total number of layers.