The chemical composition and thermal properties of natural fibers are the most critical variables that determine the overall properties of the fibers and influence their processing and use in different sustainable applications, such as their conversion into bioenergy and biocomposites. Their thermal and mechanical properties can be estimated by evaluating the content of cellulose, lignin, and other extractives in the fibers. In this research work, the chemical composition and thermal properties of three fibers, namely bagasse, kenaf bast fibers, and cotton stalks, were evaluated to assess their potential utilization in producing biocomposites and bioenergy materials. The chemical composition analysis followed the Technical Association of the Pulp and Paper Industry Standards (TAPPI) methods. The total phenol content was quantified using the Folin-Ciocalteu method, while Fourier Transform Infrared Spectroscopy (FTIR) was employed to assess the light absorption by the bonds. To evaluate thermal stability and higher heating values, Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), and bomb calorimetry were performed. The chemical analysis revealed that bagasse contained 50.6% cellulose and 21.6% lignin, kenaf bast fibers had 58.5% cellulose and 10% lignin, and cotton stalks exhibited 40.3% cellulose and 21.3% lignin. The FTIR curves demonstrated a notable similarity among the fibers. The TGA analysis showed degradation temperatures of 321°C for bagasse, 354°C for kenaf bast fibers, and 289°C for cotton stalks. The DSC analysis revealed glass transition temperatures of 81°C for bagasse, 66.3°C for cotton stalks, and 64.5°C for kenaf bast fibers. The higher heating values were measured as 17.3, 16.6 and 17.1 MJ/kg for bagasse, kenaf bast fibers, and cotton stalks, respectively. The three fibers have a high potential for biocomposites and bioenergy material manufacturing.