The conversion of lignocellulosic biomass into renewable bioproducts requires a pretreatment step to disrupt the cell matrix, thereby facilitating the access of hydrolytic enzymes to the cellulosic. Although several studies have examined pretreatment with the ionic liquid; triethylammonium hydrogen sulfate [TEA][HSO₄] in sugarcane bagasse (SB) and straw (SS). This study aimed to evaluate the fractionation of SB and SS using [TEA][HSO₄], focusing on the recovery of lignin and cellulose pulp. The methodology involved the synthesis of [TEA][HSO₄] and the application in the pretreatment of SB and SS, both in their raw forms and after hydrothermal pretreatment (HP). The lignins and cellulose pulps were recovered and characterized chemically and structurally. The cellulose pulp was subjected to enzymatic hydrolysis using the commercial enzymatic preparation Cellic™ CTec II. Pretreatment with [TEA][HSO₄] demonstrated selectivity in the removal of lignin and hemicellulose, resulting in enriched cellulose pulps. The recovered lignins showed an average yield of 75%, exhibited 85% purity and showed well-defined aromatic bands, characteristic of grass lignins, indicating structural preservation. Thermogravimetric analysis revealed similar decomposition profiles between lignins, with thermal stability influenced by reaction time. The lignins presented average molar masses (Mn=3.5-4.6 kDa) and low polydispersity. Pretreatment with [TEA][HSO₄] significantly increased cellulose-to-glucose conversion during enzymatic hydrolysis, reaching values of 60-80%. Overall, the results highlight the potential of [TEA][HSO₄] for the efficient fractionation of SB and SS confirming their identity as being close to native biomass lignin, distinguishes them from Kraft lignin and reinforces their potential for higher-value applications