This paper evaluates a novel biorefinery approach for the conversion of lignocellulosic biomass from pinewood. A combination of thermochemical and biochemical conversion was chosen with the main product being ethanol. Fast pyrolysis of lignocellulosic biomasss with fractional condensation of the products was used as the thermochemical process to obtain a pyrolysis-oil rich in anhydro-sugars (levoglucosan) and low in inhibitors. After hydrolysis of these anhydro-sugars, glucose was obtained which was successfully fermented, after detoxification, to obtain bioethanol. Ethanol yields comparable to traditional biochemical processing were achieved (41.3% of theoretical yield based on cellulose fraction). Additional benefits of the proposed biorefinery concept comprise valuable by-products of the thermochemical conversion like bio-char, mono-phenols (production of BTX) and pyrolytic lignin as a source of aromatic rich fuel additive. The inhibitory effect of thermochemically derived fermentation substrates was quantified numerically to compare the effects of different process configurations and upgrading steps within the biorefinery approach. (C) 2014 Elsevier Ltd. All rights reserved.