A phenomenological model for elucidating phase diagrams of hexagonal columnar/nematic liquid crystal mixtures has been developed on the basis of the combination of the Flory-Huggins (FH) free energy of isotropic mixing, Maier-Saupe (MS) free energy for nematic ordering, and Chandrasekhar-Clark free energy for hexagonal ordering. Self-consistent calculations show the theory is capable of predicting the various phase diagrams, covering nematic, hexagonal columnar, and isotropic phases. The model has been tested with the eutectic phase diagram of hexagonal columnar liquid crystal, 2, 3, 6, 7, 10, 11-hexapentyloxy triphenylene (HPTP)/reactive nematic mesogens, 4-(3-acryloyloxypropyloxy)-benzoic acid 2-methyl-1, 4-phenylene ester (RM257) mixtures determined by using DSC, polarized optical microscope (POM), and wide-angle X-ray diffraction (WAXD). The self-consistent calculation displays isotropic (I), nematic (N), hexagonal columnar (Colh), N + I, and Colh + I, and Colh + N coexistence regions. These phase regions has been confirmed by thermal quenching various compositions from the isotropic melt to different phase regions. Guided by the established phase diagram of HPTP/RM257 mixtures, photo-polymerization of the mixture has been carried out in different phase regions. The as-cured HPTP/p-(RM257) composites fabricated at isotropic phase (130 °C) remains single isotropic phase under optical microscope, whereas the SEM and TEM results show the bead-like microstructure with sub-micrometer scale. Polymerization-induced mesophase transition experiments have been carried out at isotropic temperatures slightly above the clearing point of the mixtures. Of particular interest is the development of liquid crystalline spherulites. Moreover, the fixation of the morphology is observed when the photopolymerization is carried out in the N, N + I, and N + Colh region. A generalized thermodynamic model for describing smectic A and smectic B ordering has been developed based on Chandrasekhar-Clark and Maier-Saupe-McMillan theories by introducing hexagonal and layered order parameters. By combining the proposed model with Flory-Huggings theory, the total free energy for induced smectic phase in binary nematic liquid crystal mixtures has been obtained. The calculated phase diagram has been tested with the induced smectic B phase diagram of binary nematic liquid crystal mixtures of 4'-n-pentyl-4- cyanobiphenyl (5CB)/4'-methoxy- benzylidene-4-butylaniline (MBBA) and the induced smectic A phase diagram of 4-cyano-4'-pentyloxy biphenyl (5OCB) and 4-pentylphenyl-4'- heptyloxybenzoate (7O5) mixtures. Our calculation results show the remarkable agreement with the experimental data in the reported literature.