Pectinolytic enzymes, steam explosion and alkaline treatment were used to assess the role of pectin for the accessibility of hydrolytic enzymes in the enzymatic hydrolysis of biomass. Hemp (Cannabis sativa L.), a potential energy crop especially in boreal climate with a low need of fertilizers, was used in the study either as untreated or anaerobically preserved raw material. Addition of pectinases increased the hydrolysis yield by 26%, 54%, and 64% from the theoretical carbohydrates of untreated, acid, and alkali-preserved materials, respectively. Steam explosion and hot alkali treatment increased the conversion of the total carbohydrates by 78% and 60%, respectively, compared to the untreated hemp. Elevated separation of cells within the hemp stalk tissues and an increased surface area was revealed after hot alkali or pectinase treatments, contributing to the increased conversion to sugars by commercial enzymes. (C) 2011 Elsevier Ltd. All rights reserved.