Agricultural crop wastes are typically lignocellulosic in composition and thus partially recalcitrant to enzymatic degradation. The recalcitrant nature of plant biomass and the inability to obtain complete enzymatic hydrolysis has led to the establishment of various pre-treatment strategies. Alkaline pre-treatments increase the accessibility of the exposed surface to enzymatic hydrolysis through the removal of acetyl and uronic acid substituents on hemicelluloses. Unlike the use of steam and acid pre-treatments, alkaline pre-treatments (e.g. lime) solubilise lignin and a small percentage of the hemicelluloses. The most common alkaline pre-treatments that are employed make use of sodium hydroxide and lime. This study compared the synergistic degradation of un-treated and lime pre-treated sugarcane bagasse using cellulosomal and non-cellulosomal hemicellulases as free enzymes. The enzyme combination of 37.5% ArfA and 62.5% ManA produced the highest amount of reducing sugar of 91.834μmol/min for the degradation of un-treated bagasse. This enzyme combination produced a degree of synergy of 1.87. The free enzymes displayed an approximately 6-fold increase in the enzyme activity, i.e. the total amount of reducing sugar released (593.65μmol/min) with the enzyme combination of 37.5% ArfA, 25% ManA and 37.5% XynA for the lime pre-treated substrate and a degree of synergy of 2.14. To conclude, this study indicated that pre-treating the sugarcane bagasse is essential, in order to increase the efficiency of lignocellulose enzymatic hydrolysis by disruption of the lignin sheath, that the lime pre-treatment did not have any dramatic effect on the synergistic relationship between the free enzymes, and that time may play an important role in the establishment of synergistic relationships between enzymes.