This paper investigates the non-isothermal thermokinetics of the co-pyrolysis of sugarcane bagasse and corn residue blended with coal. The individual devolatilization behaviour of each of the fuels obtained separately was compared with the behaviour of the biomass blends with coal at various mix ratios. Possible synergistic behaviour that points to the existence of chemical interactions during pyrolysis between the coal and biomass fractions of the blends could thus be quantified. Synergistic interactions in the blends resulted in higher than expected volatile yields. The interactions occurred between 300 degrees C and 500 degrees C, corresponding to the end of biomass devolatilization and the start of coal decomposition. Isoconversional kinetic analysis revealed that apparent activation energy values varied between 165-180, 162-190, 160-175, and 225-260 kJ mol(-1) for sugarcane bagasse, corn cobs, corn stover, and coal in the 0.1 to 0.8 conversion range. A comparison of E(alpha) for single fuels and coal-biomass blends gave further evidence of synergistic behaviour as demonstrated by larger variation in E(alpha) during the decomposition of the blends, compared to the individual fuels. (C) 2012 Elsevier B.V. All rights reserved.