Due to biomass recalcitrance, including complexity of lignocellulosic matrix, crystallinity of cellulose, and inhibition of lignin, the bioconversion of lignocellulosic biomass is difficult and inefficient. The aim of this study is to investigate an effective and green pretreatment method for overcoming biomass recalcitrance of lignocellulose. An effective mechanical activation (MA) + metal salt (MAMS) technology was applied to pretreat sugarcane bagasse (SCB), a typical kind of lignocellulosic biomass, in a stirring ball mill. Chlorides and nitrates of Al and Fe showed better synergistic effect with MA, especially AlCl3, ascribing to the interaction between metal salt and oxygen-containing groups induced by MA. Comparative studies showed that MAMS pretreatment effectively changed the recalcitrant structural characteristics of lignocellulosic matrix and reduced the inhibitory action of lignin on enzymatic conversion of SCB. The increase in hydroxyl and carboxyl groups of lignin induced by MAMS pretreatment led to the increase of its hydrophilicity, which could weaken the binding force between cellulase and lignin and reduce the nonproductive binding of cellulase enzymes to lignin. MAMS pretreatment significantly enhanced the enzymatic digestibility of polysaccharides substrate by overcoming biomass recalcitrance without the removal of lignin from enzymatic hydrolysis system.