Novel multilayer formation of fluorocarbon compounds at the hexane/water interface was investigated from the viewpoint of intermolecular interaction and miscibility of molecules in the adsorbed film. The two kinds of mixed systems were employed: 1H,1H,2H,2H-perfluorododecanol (FC12OH)-1H-perfluorodecane (HFC10) (System A) and 1-icosanol (C20OH)-HFC10 (System B). The interfacial tension γ between the hexane solution and water was measured as a function of total concentration m and the composition of HFC10 in the mixture X(2) at 298.15 K under atmospheric pressure. X-ray reflectivity (XR) measurement was performed at BL37XU in SPring-8 as a function of scattering vector Q(z). In both systems, the γ vs m curves except for the pure HFC10 system have a break at low concentrations, which corresponds to the gaseous-condensed monolayer transition for System A and the expanded-condensed monolayer for System B. The remarkable difference between the two systems was that the curves in a limited bulk composition range (0.45 ≤ X(2) ≤ 0.9) of System A show another break at high concentrations close to the solubility limit. The total interfacial density above this break point was around 7-11 μmol m(-2), suggesting the spontaneous molecular piling to form a multilayer. The phase diagrams of adsorption in the condensed monolayer indicated that the film composition of HFC10 is negative in System B but definitely positive above X(2) ≥ 0.45 in System A. This clearly shows that HFC10 molecules are miscible with FC12OH but immiscible with C20OH in the condensed monolayer. Thus, it is likely that the mixing of HFC10 with FC12OH in the condensed monolayer induces multilayer formation. The X-ray reflectivity normalized by Fresnel reflectivity R/R(F) vs Q(z) plot in the condensed monolayer of System A was fitted by a one-slab model with uniform electron density and thickness. The electron density profile was almost the same as that of the pure FC12OH system. The plot in the multilayer, on the other hand, was fitted well by the two-slab model with different electron densities and thicknesses. The electron density profile showed that the multilayer consists of two layers, one of which has slightly higher electron density than the bulk hexane phase and piles on the lower layer with almost the same electron density as the condensed FC12OH monolayer.