Developing sustainable biorefineries is an urgent matter to support the transition to a sustainable society. Lignocellulosic biomass (LCB) is a crucial renewable feedstock for this purpose, and its complete valorization is essential for the sustainability of biorefineries. However, it is improbable that a single pretreatment will extract both sugars and lignin from LCB. Therefore, a combination of pretreatments must be applied. Liquid-hot-water (LHW) is highlighted as a pretreatment for hemicellulose hydrolysis, conventionally analyzed only in terms of sugars and degradation products. However, lignin is also hydrolyzed in the process. The objective of this work was to evaluate LHW at different conditions for sugars, degradation products, and lignin. We performed LHW at 160, 180, and 200 °C for 30, 60, and 90 min using wheat straw and characterized the extract for sugars, degradation products (furfural, hydroxymethylfurfural, and acetic acid), and lignin. Three conditions allowed reaching similar total sugar concentrations (~12 g/L): 160 °C for 90 min, 180 °C for 30 min, and 180 °C for 60 min. Among these, LHW performed at 160 °C for 90 min allowed the lowest concentration of degradation products (0.2, 0.01, and 1.4 g/L for furfural, hydroxymethylfurfural, and acetic acid, respectively) and lignin hydrolysis (2.2 g/L). These values indicate the potential use of the obtained sugars as a fermentation substrate while leaving the lignin in the solid phase for a following stage focused on its extraction and valorization.