Pineapple residue and banana pseudo-stem are waste from agricultural production in tropical zones, and the characteristics of their pyrolysis should be explored for high-value utilization. Kinetics, thermodynamics, reaction mechanism and valorization of bio-char during pyrolysis of these feedstock were conducted in this study. In biomass mainly decomposed at 150–500 °C, there was a significant mass loss peak for banana pseudo-stem at 650 °C. The activation energy range of pineapple residue and banana pseudo-stem, based on a multi-heating rate method, was 159–335 and 169–364 kJ/mol, respectively. Based on the Gaussian multi-peak fitting method, derivative thermogravimetric curves of pineapple residue and banana pseudo-stem were deconvoluted with three or four fitting peaks, based on the key components in biomass. Interaction between intermediates during pyrolysis increased the complexity of kinetic data. The main carbon number of organic volatiles during pyrolysis was C₄ and C₅ for pineapple residue, and C₂ and C₃ for banana pseudo-stem. The high content of cellulose and hemicellulose in biomass improved the yield of volatiles. Porous carbon sourced from pineapple residue and banana pseudo-stems had specific capacitance of 375 F/g and 297 F/g at a current density of 0.5 A/g, respectively. This suggested pineapple residue and banana pseudo-stem as a potential feedstock for electrochemical materials.