Efficient lignocellulosic fractionation and conversion into platform chemicals provide a considerable opportunity for the industrial operation of a lignocellulosic biorefinery. However, single-step pretreatments are often insufficient to overcome biomass recalcitrance as the existence of insoluble lignin generally restricts component fractionation and conversion. This study performed a two-step pretreatment, consisting of sequential liquid hot water (LHW) and green-liquor (GL), for bioprocessing of aspen biomass into bioproducts such as glucose, levulinic acid (LA), and lignin adsorbent. The two-step pretreated glucan-rich solid displayed high cellulose accessibility, which is responsible for 94% of the glucose yield. The optimized LHW pretreatment (200 °C, 40 min) solubilized 91% of the hemicellulose, which together with monomeric sugars in the hydrolysate solution was straightly heated at 190 °C for 80 min and yielded 72.49% of LA in the presence of sulfuric acid as a catalyst. Moreover, GL post-treatment (Na2CO3+Na2SO3) solution maximized the delignification at 78% from LHW pretreated substrate. The isolated lignin possessed a remarkable ability for Cd2+ and Pb2+ uptake with maximized adsorption values of 250 mg/g and 228 mg/g, respectively. Finally, energy analyses showed that moderate lignocellulosic conversion could obtain an energy recovery of 85%, providing a sustainable pathway for biorefinery approaches.