Biomass has several benefits due to its novel behavior among energy sources. This study aims to characterize a unique form of biomass from two varieties of Matooke peel, namely, untreated Mbwazirume waste peel (UM-WP) and untreated Nakyinyika waste peel (UN-WP). The analysis of the characteristics of these biomasses was carried out using TGA, SEM, and EDXS. TG and DTG analysis showed an almost identical trend between UM-WP and UN-WP. The UM-WP exhibited a high VC 69.988 wt%, MC 13.125 wt%, O 48.02 wt%, and HHV 15.52 MJ-kg −1 with a low ash content 5.957 wt%, sulfur 0.64 wt%, and N 1.13 wt% compared to UN-WP. As compared to pretreated biomass, it was found that the smaller particle sizes had only minor intra-particle gradients and the bigger particle sizes had more of a linear pattern variation. The pyrolysis behavior obtained revealed three distinct regions at elevated temperatures related to the elimination of cellulose, hemicellulose, and lignin. During carbonization, high fluidity and bubbles were produced due to the release of a large amount of volatile matter and forms porous structure which flowed through the fluid mass and produced a non-homogeneous vacuolated structure. These might cause the oxygen to easily disperse inside the particles during combustion. In addition, white spots were observed which are elements from different categories. The findings of this study indicate that UM-WP biomass could be an ideal material source for the production of biofuel and photovoltaic.