AbstractAlkaline oxidation (AlkOx) is an effective fractionation technique for lignocellulosic raw materials. The efficiency of the AlkOx treatment can further be enhanced by using a catalyst (CatOx). Both CatOx and AlkOx provide a fiber fraction containing readily hydrolysable carbohydrates that can be utilized in biotechnical processes and a liquid fraction containing solubilized lignin and reaction products from various biomass components. The effects of different fractionation conditions on yields and chemical composition of solubilized and insoluble fractions were investigated. Two temperatures and two reaction times were studied with and without a catalyst. The composition and content of carbohydrates in the fiber and liquid fractions were examined. The generation of aliphatic carboxylic acids as oxidation products was also investigated. The catalytically assisted oxidation was more efficient than the alkaline counterpart in dissolution of wood components under a four-hour treatment period resulting in higher dissolution of hemicelluloses. A longer reaction time of 20 hours leveled out the differences between the oxidation processes. Comparison of different bases showed that similar solubilisation of dry matter was obtained with NaOH, KOH, and Na2CO3. Oxidation in Na2CO3 caused higher dissolution of glucomannan and greater acid production. The dissolution of hemicellulose and lignin, and their oxidation to acids was most efficient in the first 4 hours of oxidation.