Mixtures of a sernifluorinated alkane 1, 11 1,2,2,3,3 4,4 5,516 6,7,7,8,8,9,9, 10,10-henicosafluorotriacontane (abbr. F10H20) and different alcohols were investigated at the air/water interface using surface pressure-area isotherms complemented with BAM images. In our studies, octadecanol and its fluorinated derivatives differing in the degree of fluorination were researched. To verify the influence of an iso branching of the fluorinated segment in an alcohol molecule, the properties of perfluorooctyldecanol and perfluoro-iso-nonyldecanol in mixtures with F10H20 were compared. From the isotherms datapoints, the excess of free energy of mixing (Delta G(exc)) together with the interaction parameter (a) were calculated. On the basis of the additivity rule and BAM images, phase diagrams for all of the investigated systems were constructed. It occurs that F10H20 mixes with the fully hydrogenated alcohol, octadecanol, within the whole range of alcohol mole fractions, whereas it is completely immiscible with its perfluorinated analogue. Regarding the mixtures of F10H20 with sernifluorinated alcohols. it turned out that these systems exhibit limited miscibility, i.e., are miscible at a low semifluorinated alcohol proportion, whereas upon increasing alcohol content, the systems start to demix. It may be concluded that the molecular packing in mixed monolayers is the key factor determining the miscibility of F10H20 of the investigated alcohols.