The escalating global waste crisis necessitates sustainable valorization strategies, with biochar production emerging as a promising solution for converting organic residues into a carbon-rich material. This study evaluated biochar derived from corncob and khat waste pyrolyzed using allo-thermal and auto-thermal multi-purpose stoves. Biochar was fractionated into four particle sizes (>2 mm, 1–2 mm, 0.6–1 mm, and <0.6 mm) and characterized for ash content, pH, and electrical conductivity (EC). Results demonstrated that the auto-thermal stove, operating at higher temperatures (up to 800 °C), consistently produced biochar with greater ash content (khat: 12–19%; corncob: 11–14%), alkaline pH (9.2–10.0), and significantly higher EC compared to the allo-thermal stove (maximum 350 °C). EC values ranged from 0.38 mS/cm (coarse allo-thermal corncob) to 6.6 mS/cm (fine auto-thermal khat), with auto-thermal biochar exhibiting EC values 5–10 times higher than their allo-thermal counterparts. khat waste consistently yielded biochar with higher ash content, pH, and EC than corncob, reflecting its richer mineral composition. Particle size fractionation revealed that pH and EC increased progressively with decreasing particle size across all treatments, with the finest fraction (2 mm) to 6.6 mS/cm (<0.6 mm). This study demonstrates that decentralized biochar production using multi-purpose stoves can yield materials with tunable properties, and that khat waste—an underutilized regional resource—shows particular promise for producing high-ash, high-EC biochar suitable for acidic soil amendment.