The effect of initiator and liquid crystal 4-cyano-4'-n-pentylbiphenyl (5CB) concentrations on the monomer conversion and molecular weight distributions of the polymer in the free-radical polymerization of 2-ethylhexylacrylate (2-EHA) has been studied and characterized using Fourier transform infrared spectroscopy, differential scanning calorimetry, and gel permeation chromatography. A slight effect of the concentration of the photoinitiator has been observed both on the monomer conversion and the molecular weight distribution of poly (2-EHA). Increasing the amount of 5CB in the initial mixture leads to a decrease of conversion, glass transition temperature of the polymer, molar mass of polymer and of the polydispersity.