The plant fibers are rich in cellulose and they are easily renewable source of fibers with the potential for polymer reinforcement. The presence of surface impurities and the large amount of hydroxyl groups make plant fibers less attractive for reinforcement of polymeric materials. Hemp (Cannabis sativa L.) fibers were subjected to alkalization using 1N sodium hydroxide (NaOH). The physical, chemical, and surface properties of untreated and chemically modified fibers are studied using X-ray diffraction (wide angle X-ray scattering), Fourier transform infrared spectroscopy and scanning electron microscopy (SEM), respectively. The microstructural parameters such as crystallite size < N >, lattice strain (g in %), and enthalpy ((*)) have been determined by X-ray line profile analysis using Fourier method of Warren. It was found that the crystallite size < N > decreases with the increase in treatment time. SEM study shows the fibers surface becoming rough and suitable for reinforcement.