Biogas production from lignocellulose feedstocks has become an acceptable energy source globally due to their availability and economy. Lignocellulose materials have a complex arrangement that hinders digestion during the process. Therefore, applying the pretreatment process to lower the recalcitrant properties is required to utilize the full potential of the feedstock. This study, therefore, examines the influence of the oxidative pretreatment on the microstructural arrangement and biomethane yield of Xyris capensis. Piranha solution was prepared using H2O2 and H2SO4 at 100, 95:5, 85:15, and 75:25% of H2O2: H2SO4, respectively, and Xyris capensis grass was soaked in the prepared solution. The pretreated and untreated feedstocks were examined under the scanning electron microscope (SEM) to study the effect of the pretreatment on the microstructural arrangement. The effect of the pretreatment on biomethane yield was investigated during anaerobic digestion in a laboratory-scale batch digester at a mesophilic temperature (37 °C). The SEM analysis shows that the oxidative pretreatment method significantly affects the substrate’s microstructure, and the pretreatment’s severity depends on the percentage of H2SO4 added. A biomethane yield of 174.41, 188.61, 192.23, 207.51, and 139.71 mL CH4/g VSadded was observed, and the yield was increased by between 24.84 and 48.52% compared to the untreated substrate. Therefore, applying oxidative pretreatment using low-cost H2O2 is a clear method of improving the biomethane yield of lignocellulose feedstocks.