The presented results of research on the effectiveness of enzymatic hydrolysis of lignocellulosic waste, depending on their initial depolymerisation in alkaline medium were considered in the context of the possibility of their further use in the fermentation media focused on the recovery of energy in the form of molecular hydrogen. The aim of this study was to determine the appropriate dose and concentration of a chemical reagent, whose efficiency would be high enough to cause decomposition of the complex, but without an excessive production of by-products which could adversely affect the progress and effectiveness of the enzymatic hydrolysis and fermentation. The effect of treatment on physical-chemical changes of homogenates’ properties such as pH, COD, the concentration of monosaccharide and total sugars and the concentration of total suspended solids and volatile suspended solids was determined. The enzymatic decomposition of lignocellulosic complex was repeatedly more efficient if the sample homogenates were subjected to an initial exposure to NaOH. The degree of conversion of complex sugars into simple sugars during enzymatic hydrolysis of homogenates pre-alkalized to pH 11.5 and 12.0 was 83.3 and 84.2% respectively, which should be sufficient for efficient hydrogen fermentation process.