Plant-derived biopolymers are renewable and readily available, thus making viable alternatives to synthetic polymers. The present study examined properties of biopolymers from cover crops such as rye, oat, clover, vetch, and barley, which were grown organically in a greenhouse. The yields of cellulose, hemicellulose, and lignin of the cover crops were calculated based on the dry weight. Structural variations and thermal properties of the isolated cellulose were characterized and compared with commercial cellulose using Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, and Thermogravimetric analysis (TGA). The average yield percentages of cellulose, hemicellulose, and lignin were 19 to 27%, 9 to 25%, and 1.42 to 4.86%, respectively. The FTIR and Raman spectral analysis indicated that the isolated cellulose had similar peaks and patterns to commercial cellulose, and confirmed the removal of non-cellulosic constituents. The onset decomposition temperature occurred at 270 °C in all samples. Interestingly, the maximum degradation temperature beyond 370 °C in cellulose was isolated from black oat, which was higher than commercial cellulose (350 °C). The findings of this research suggest that cellulose isolated from cover crops may be a benefit to the polymer industry in the development of bio-based materials such as biofuels, bio-composites, and biomedical devices.