This work studied the fractionation of sugarcane bagasse via Organosolv treatment using isopropanol/water in the presence of Raney-Ni and molybdenum carbide catalysts (Bulk Mo2C and Mo2C supported on activated carbon (AC) or Al2O3). The degree of delignification, the bio-oil and solid residue composition depended on the type of catalyst. A partial extraction of hemicellulose occurred followed by depolymerization, resulting in a product distribution that depended on the catalyst. Raney-Ni catalyst promoted the formation of diols and triols, while xylose, furfural, and furan were mainly produced by Mo2C based-catalysts. The Organosolv treatment without catalyst and in the presence of bulk Mo2C produced a bio-oil containing mainly 2,3-dihydrobenzofuran. Mo2C/AC and Mo2C/Al2O3 are promising catalysts for the fractionation of sugarcane bagasse that produced a bio-oil with higher yield to substituted methoxyphenols and a solid residue more easily hydrolyzed by cellulases, producing higher yield to glucose than Raney-Ni catalyst.