This research evaluated the effect of different delignification pretreatments (enzymatic and organosolv), on the crystallinity and enzymatic hydrolysis of harvested sugar cane residues. The Crystallinity Index (CrI), the Relative Number of Intensity (Ir), the degree of cellulose mercerization (IIC-%), and the Global Index of Saccharification (GIS) were used as measurement parameters for six different substrates obtained from sugar cane residues (tops and leaves) by different processes. In this characterization, the spectroscopic ty Techniques of Fourier Transform infrared spectroscopy (FTIR), X-ray diffraction and scanning eElectron microscopy (SEM) were used. Substrates to which only organosolv pretreatment was applied, without any further treatment, presented good behavior for the enzymatic hydrolysis and a high CrI, possibly due to the increase of the crystallinity by elimination of amorphous material.