Kenaf fibers, cellulose-based natural fibers, were used as precursor for preparing kenafbased carbon fibers. The effects of carbonization temperature (700oC to 1100oC) and chemical pre-treatment (NaOH and NH4Cl) at various concentrations on the thermal change, chemical composition and fiber morphology of kenaf-based carbon fibers were investigated. Remarkable weight loss and longitudinal shrinkage were found to occur during the thermal conversion from kenaf precursor to kenaf-based carbon fiber, depending on the carbonization temperature. It was noted that the alkali pre-treatment of kenaf with NaOH played a role in reducing the weight loss and the longitudinal shrinkage and also in increasing the carbon content of kenaf-based carbon fibers. The number and size of the cells and the fiber diameter were reduced with increasing carbonization temperature. Morphological observations implied that the micrometer-sized cells were combined or fused and then re-organized with the neighboring cells during the carbonization process. By the pre-treatment of kenaf with 10 and 15 wt% NaOH solutions and the subsequent carbonization process, the inner cells completely disappeared through the transverse direction of the kenaf fiber, resulting in the fiber densification. It was noticeable that the alkali pre-treatment of the kenaf fibers prior to carbonization contributed to the forming of kenaf-based carbon fibers.