The consolidation of different polymeric bioconstituents was clearly observed in briquetted biofiiel produced from pigeon pea crop residues. Critical thermogravimetric diagnosis showed that the scattering of tail end segments of thermograms taken at different heating rates was remarkably low in briquetted biofiiel as compared to the scattering in raw material. The consolidation of polymeric cellulose and lignin was discussed and explained. Kinetics was evaluated using isoconversional integral Ozawa-Flynn-Wall method. The activation energy profile of briquetted biofuel dominated over the raw pigeon pea stalks showing higher thermal stability, which was evidence, positive toward the consolidation of intrinsic biopolymers due to briquetting process.