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Generating electricity from biomass combustion is an essential means of supporting basic demands in deprived regions, including lighting, communication, and medical care. In this work, a high-capacity portable biomass-combustion-powered thermoelectric generator (BCP-TEG) is developed and tested. Temperature distribution, power load feature, efficiencies at different levels, and a field test are comprehensively explored. The results show that the proposed 7.6 kg BCP-TEG can cogenerate a heating power of 750 W and an electric power of 23.4 W, corresponding to a combined heat and power (CHP) efficiency of 32.3%. The net power density of 2.41 W·kg−1 is much greater than those in previous reports based on water closed-loop cooling. Furthermore, this study demonstrates that a 3.7 V battery of 6.2 A·h can be fully charged by burning 1 kg of wood sticks. Finally, we provide a comprehensive discussion identifying existing issues and future opportunities in this field.