Internal structural and dynamics of untreated and the enzyme treated natural cellulose were studied by C-13 cross polarization magic angle spinning (CP-MAS) solid state Nuclear Magnetic Resonance (SSNMR) spectral analysis and relaxation measurements. C-13 spectral analysis indicates the susceptible degradation of the amorphous region of cellulose-microfibril due to enzyme-treatment. Spin-lattice relaxation time of chemically different carbon sites is decreased in enzyme-treated cellulose, which suggests that the polysaccharide chain becomes depolymerised. Relaxometry measurement also suggests that rice straw is more susceptible for degradation than sugar cane bagasse.