Experimental studies of phase diagram and morphology of mixtures composed of linear poly(2-ethylhexylacrylate) (poly-2EHA) of molecular weight Mw=92000g/mol and E7, an eutectic blend of nematic liquid crystals (LCs), were performed. The latter consists of four cyanoparaphenylenes i.e. 4-cyano-4’-n-pentyl-biphenyl (5CB), 4-cyano-4’-n-heptyl- biphenyl (7CB), 4-cyano-4’-n-oxyoctyl-biphenyl (8OCB), and 4-cyano-4’’-n-pentyl-p-biphenyl (5CT). Thermal properties of the poly-2EHA/E7 system were studied by differential scanning calorimetry and the sample morphologies were investigated by optical microscopy. Phase diagram analysis revealed an increase of the nematic-isotropic transition temperature when E7 was added to poly-2EHA, compared to pure E7. This effect, related to a preferential miscibility phenomenon of E7 components towards poly-2EHA, was evidenced by gas chromatography analysis coupled to mass spectrometry (GC-MS), allowing to qualify and quantify the content of phase separated LC domains. Thermograms of model LC mixtures including 5CB, 7CB, 8OCB and 5CT, which correspond to their composition in segregated LC domains of poly-2EHA/E7, present strong deviations from eutectic behavior. In order to access the impact of such variations for practical applications, such a model LC mixture was introduced in photochemically crosslinked 2-EHA (polycross-2EHA). Surprisingly, the electro-optical response of the obtained polycross-2EHA/LC films was considerably improved compared to the original polycross-2EHA/E7 system.