A hybrid purification process combining extraction and distillation for the production of levulinic acid (LA), furfural, and formic acid (FA) from lignocellulosic biomass was studied. The effective process depends on the choice of appropriate extraction solvent. A comprehensive procedure of solvent selection for the LA production process was developed. A range of solvents were first evaluated by solvent screening, and processes using the three most promising solvents, including methyl isobutyl ketone (MIBK); furfural and octanol were then designed and optimized using an Aspen Plus simulator. These processes were evaluated in terms of the energy consumption, total annual cost, and environmental impact. As a result, MIRK showed the most favorable equilibrium for the extraction of LA but was unfavorable for FA extraction. Octanol showed not only the most favorable result in the extraction of FA, but was also favorable for the extraction of furfural and LA. Interestingly, furfural could extract more LA than octanol and extract more FA than MIBK. The design results show that the furfural solvent process can reduce energy consumption by up to 25.2% and 21.4%, the TAC by up to 30.6% and 25.9%, and CO2 emissions by up to 27.0% and 25.5% compared to processes using octanol and MIBK as solvents, respectively.