The goals of this work are to obtain thermoplastic starch (TPS) with different glycerol/water ratios, verify its characterization by different techniques, and study the influence of addition of cellulose nanofibers in the matrix of TPS. The general procedure for processing starchy materials involves granular alteration with the combination of temperature, shear, and plasticizers. Distilled water and glycerol are used as plasticizers, and the influence of both of them has been studied in tensile properties. By infrared spectroscopy analysis, the addition of plasticizers created new physical links (hydrogen bonds) with starch molecules thereby shifting the characteristic peaks of native corn starch to higher wave number. The most suitable composition for the elaboration of bionanocomposites has been determined and bionanocomposites with different content of cellulose nanofibers have been obtained and their mechanical properties have been studied.