The effect of prewashing process prior to the liquid hot water (LHW) pretreatment of high free ash content waste wheat straw (WWS) was investigated. It was found that prewashing process decreased the ash content of WWS greatly, from 29.48% to 9.82%. This contributed to the lower pH value of prehydrolyzate and higher xylan removal in the following LHW pretreatment. More importantly, the prewashing process effectively increased the cellulose enzymatic hydrolysis efficiency of pretreated WWS, from 53.04% to 84.15%. The acid buffering capacity (ABC) and cation exchange capacity (CEC) of raw and prewashed WWS were examined. The majority of free ash removal from WWS by prewashing resulted in the decrease of the ABC of the WWS from 211.74 to 61.81 mmol/pH-kg, and potentially enhancing the efficiency of the follow-up LHW pretreatment. (C) 2016 Elsevier Ltd. All rights reserved.