In this study, the potential of organic acids (formic acid, acetic acid) in a catalytical and mechanocatalytic conversion of lignocellulosic barley straw to valuable sugars is explored using sulfuric acid as a reference. Acid-catalyzed hydrolysis has been carried out with acid-impregnated samples as well as unmodified barley straw. In the mechanocatalytical approach, pretreatment consists of impregnation with the acid catalyst and mechanical treatment by ball milling following chemical hydrolysis. Straw samples and residues were analyzed by Fourier transform infrared spectrometry (FT-IR) whereas hydrolysate analysis was based on total reducing sugar (TRS) determination following the DNS method and capillary electrophoresis (CE) analysis. The results indicated that acetic acid and formic acid are rather mild acids yielding low TRS levels compared to the reference acid. Mechanocatalytical pretreatment slightly increased TRS yields, but not significantly. Strikingly, sulfuric acid showed an efficient conversion efficiency yielding almost 45% of TRS. Furthermore, this study provided evidence for the acetylation of straw components when acetic acid was used as catalyst. Alkali hydrolysis induced the de-esterification, but revealed no significant increase of TRS yields. (C) 2016 Elsevier Ltd. All rights reserved.