The present article describes the experimental and theoretical observations on the formation of holographic, polymer-dispersed, liquid crystals and electrically switchable, photonic crystals. A phase diagram of the starting mixture of nematic liquid crystal and photo-reactive triacrylate monomer was established by means of differential scanning calorimetry (DSC) and cloud point measurement. Photolithographic patterns were imprinted on the starting mixture of LC/triacrylate via multi-beam interference. A similar study was extended to a dendrimer/ photocurative mixture as well as to a single component system (tetra-acrylate). Theoretical modeling and numerical simulation were carried out based on the combination of Flory-Huggins free energy of mixing and Maier-Saupe free energy of nematic ordering. The combined free energy densities were incorporated into the time-dependent Ginzburg-Landau (Model C) equations coupled with the photopolymerization rate equation to elucidate the spatio-temporal structure growth. The 2-D photonic structures thus simulated were consistent with the experimental observations. Furthermore, 3-D simulation was performed to guide the fabrication of assorted photonic crystals under various beam-geometries. Electro-optical performance such as diffraction efficiency was evaluated during the pattern photopolymerization process and also as a function of driving voltage.