Urban organic wastes (UOW) strain the infrastructures for solid waste treatment (SWT) in emerging economies. This study investigated biochar gained from three major UOW sources in India—banana peduncles (BP), a fibrous waste, from fruit markets; sewage sludge (SS) from wastewater treatment plants; and anaerobic digestate (AD) from food and market waste processing facilities—in terms of its potential to sequester and become long-term carbon sink in soils. Herein, the chemical properties (using ATR-FTIR) and thermal oxidative stability (using TGA) of biochars derived from these UOW and their three blends were examined. Biochar from SS and AD and the blends were found to possess more ash content, Cl, and alkali and alkaline earth metals (AAEM) than that from BP. The conventional recalcitrance index (R50) could not quantify and compare the stability of these mineral- and ash-rich biochars. Hence, a modified thermal oxidative recalcitrance index (TORi) is proposed. All the biochar from blends prepared at highest treatment temperature of 650 °C shows similar aromaticity. However, biochar from blend of 50% SS, 30%BP, and 20% AD exhibits the highest recalcitrance (TORi = 0.193) to become a long-term carbon sink in soil. More than aromaticity, the influence of Si, Fe, and AAEM on the biochar matrix affects its recalcitrance. Variations in the structural properties and recalcitrance of biochars from blends are attributable to the synergy among their constituents SS, AD, and BP. The determined TORi confirms the potential of biochar from the blends of UOW as a long-term carbon sink. © 2020, The Author(s).