The mixing behavior of deuterated polydimethylsiloxane (PDMSd) and cellulose acetate butyrate (CAB) spread as Langmuir films at the air water interface was studied by means of surface pressure area isotherms, Brewster angle microscopy (BAM) observations, and in situ neutron reflectivity. The contrast variation method was used with different D2O/H2O mixtures as subphase, allowing contrast matching to either CAB, PDMSd, or PDMSd/CAB mixed film if homogeneous. At PDMSd volume fractions Phi lower than 0.6, the mixed film is a homogeneous monolayer throughout the film compression, in agreement with the monophasic film observed by BAM and the attractive interactions between PDMSd and CAB evidenced from the isotherm measurements. In contrast, at PDMSd volume fractions Phi higher than 0.6, a vertically segregated structure of the mixed film is highlighted. Indeed, whatever the surface pressure, a bilayer structure is observed with a PDMSd layer in contact with the air over a thin CAB layer in contact with the subphase. These results show that the structure of the film is mainly driven by the PDMSd volume fraction which allows obtaining either a homogeneous membrane which composition can be tuned or a vertically segregated system. In contrast, only the thickness of the layers varies with the surface pressure while the structure of the film is not affected.