Through alkali treatment, bleaching, and sulfuric acid hydrolysis, cellulose nanocrystals (CNCs) were prepared from kenaf fibers and were used as reinforcement materials in biocomposites based on κ-carrageenan. Biocomposites in the form of films were prepared by solution casting of a mixture of κ-carrageenan, glycerol, and various amounts of CNCs (0 to 8 wt%). Fourier transform infrared spectroscopy (FTIR) revealed that alkali treatment followed by bleaching totally removed lignin and hemicellulose from the kenaf. Morphological analysis of the fibers, cellulose, and κ-carrageenan of biocomposite films were carried out using field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). The effects of filler content on the mechanical and thermal stability of the k-carrageenan biocomposite films were analyzed through tensile strength measurements and thermogravimetric analysis (TGA). At an optimum CNC content of 4%, the κ-carrageenan biocomposite films showed good dispersion, superior mechanical properties, and improved thermal stability.