We recently reported an onenzymatic biomass deconstruction process for producing carbohydrates using homogeneous mixtures of g-valerolactone (GVL) and water as as olvent. Ak ey step in this process is the separation of the GVL from the aqueous phase, enabling GVL recycling and the production of ac oncentrated aqueous carbohydrate solution.I nt his study, we demonstrate that phenolic solvents-sec-butylphenol, nonylphenol, and lignin-derived propylg uaiacol-are effective at separating GVL from the aqueous phase using only small amountso fs olvent (0.5 gp er go ft he originalw ater,G VL, and sugar hydrolysate). Furthermore, using nonylphenol, we produced ah ydrolysate that supported robustg rowth and high yields of ethanol (0.49 gE tOH per gg lucose) at an industrially relevant concentration (50.8 gL À1 EtOH). These resultss uggest that using phenolic solvents could be an interesting solution for separating and/or detoxifying aqueous carbohydrate solutions produced using GVL-based biomass deconstruction processes.Lignocellulosic biomass is emerging as ap otentialr enewable feedstock to replace crude oil as as ource of fuels and commodity chemicals. For this reason,t argeted upgrading routes are being sought to convert biomass to these valuablep roducts. In this context, soluble carbohydrates are an attractive intermediate for biomass upgrading. By weight, structuralp olysaccharides typically represent between 60 and 80 wt %o f lignocellulosic biomass.I na ddition, many chemical [1][2][3][4] and biological [5][6][7][8] processes exist for upgrading carbohydrates to fuels and chemicals.Different strategies exist for deconstructing biomass hemicellulose (a polymer of C 5 sugars; mostly xylose) and cellulose (a polymer of cellobiose, ad imer of glucose) to their soluble counterparts. Concentrated mineral acids such as sulfuric or hydrochloric acid have been used to hydrolyze hemicellulose and cellulose to soluble oligomers almost quantitatively. [9][10][11][12][13] Recently,atwo-stage process consisting of at hermochemical or pretreatment stage followed by enzymatic hydrolysis has been one of the most prominently researched biomass depolymerization methods. [14][15][16][17] Both of these methods can achieve soluble carbohydrate yields upwards of 90 %a nd produce concentrated solutionso fc arbohydrates (> 100 gL À1 ). [10,13,18] Ionic liquids are also attractive solvents for cellulose dissolution and soluble carbohydrate production. [19,20] Although these processes can be used to produce sugars from biomass,t he cost of producing and/or recovering the enzyme, mineral acid, or solvent still represents as ignificant portion of the final process. [21][22][23] For this reason,a lternate systems using significantly less catalyst have also been explored, including dilute acid hydrolysis [24,25] or hydrothermalb iomass depolymerization. [13,[26][27][28] However,a tm ost temperatures (below 510-570 K) and low acid contents( >3%), the rate of sugar degradation and dehydration to furans or other degradation products is of the sam...