Lignocellulosic biomass is the most abundant organic raw material in the world. Cellulose and hemicellulose from plants and other biomass can be hydrolyzed to produce sugars. Native lignocellulosic biomass provides limited accessibility to cellulase enzymes due to structural features. The investigations were carried out with waste lignocellulosic raw material, consisting of maize stalks and cobs. Enzyme hydrolysis was performed after acid hydrolysis with a cellulasic product. It was established that the enzyme stage, as a first treatment phase, was inefficient. It was found that cellulase activity was considerably improved after acid hydrolysis of a crushed mass. A two-stage process with acidic and then enzyme hydrolysis method was most efficient and promising for obtaining sugars for ethanol production.