Natural fibers are desirable in composite applications for their sustainability. However, improving upon the interfacial adhesion between the fiber and matrix is a major challenge. Chemical surface modification is a method used to improve compatibility of the fiber by exposing or adding functionalities to the surface, and removing non-cellulosic components in order to enhance mechanical and thermal properties. Switchgrass, an abundant natural fiber, has potential for use as a reinforcing material in composite applications. Surface modifications were conducted on switchgrass via alkali and peroxide bleaching treatments in order to remove surface impurities and create a rougher surface, as observed in scanning electron micrographs. Fourier transform infrared spectroscopy and compositional analysis showed that non-cellulosic components were reduced following the alkali and bleach treatments. Reduction of hemicellulose and lignin improved thermal stability by increasing the onset temperature of degradation from 258 °C to 289 and 281 °C for alkali and bleach treatments, respectively. The crystallinity index (CI) of untreated and treated fibers was calculated from x-ray diffraction analyses. An increase of 48% and 38% for the alkali and bleach treated fibers, respectively, was seen in the CI, compared to the untreated switchgrass. The surface of switchgrass was successfully modified using alkali and peroxide bleach treatments for composite applications.