This work presents the results of phase behavior studies of two-dimensional (2D) binary systems involving semifluorinated alkanes (SFAs) and fatty alcohols. Four different SFAs were selected for investigations: (i) with a short and branched perfluorinated moiety (iF3H20), (ii) with a short and normal perfluorinated chain (F4H20), (iii) with a long and branched perfluorinated fragment (iF9H20), and (iv) with a long and normal perfluorinated group (F10H20). Two alcohols were selected to mix with the above-mentioned SFAs: tetradecanol and docosanol. The measurements were based on surface pressure/area isotherms in addition to Brewster angle microscope (BAM) imaging. Dependencies of the collapse surface pressure and the compression modulus vs the monolayer composition together with the excess free energy of mixing values, complemented with BAM images, enabled us to draw some general conclusions regarding the phase behavior of the investigated mixed systems. Generally, it has been noticed that the addition of docosanol into an SFA monolayer exerts a condensing effect, contrary to tetradecanol. Moreover, SFAs with a long perfluorinated segment mix to a larger extent with alcohols as compared to their analogues having a short perfluorinated moiety. The resultant phase diagrams for all the investigated eight mixtures are presented and discussed.