The current study investigated a green method for alpha-arylation of a primary nitrile. Compounds possessing a benzylic nitrile have shown to exhibit biological activity. Laccases (benzenediol:oxygen oxidoreductase EC 1.10.3.2) were used as the catalysts to perform the cross-coupling reaction between benzoylacetonitrile and substituted hydroquinones. The corresponding 2-substituted 3-oxo-3-phenylpropanenitriles where synthesized in moderate to excellent yields in pH 7.0 buffered water under mild conditions. The substituent on the hydroquinone had a significant impact on product yields and regioselectivity of reaction. The use of laccases, which require O-2 as their only co-substrate and produce H2O as their only by-product, to perform this transformation is an environmentally benign method for alpha-arylation of primary nitriles. (C) 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.