Large-scale production of biomass-derived fuels and chemicals requires the economical and efficient depolymerization of lignocellulosic biomass into sugars and fuels. Catalytic hydrolysis of raw wheat straw for the production of glucose was conducted using a designed porous membrane-based polymeric solid acid catalyst consisting of poly (ionic liquid) and polysulfonic acid chains. The catalyst demonstrated superior activity and selectivity with glucose yield reached over 50% from the un-pretreated raw straw. Under the optimal conditions, over 80% of cellulose and over 90% of xylan were converted to soluble sugars and furans with over 60% glucose or xylose yields reached respectively from pretreated straw biomass. Our catalyst demonstrates high glucose and total reducing sugar (TRS) yields from lignocellulosic biomass with promising application for the future lignocellulosic biorefinery.