Conversion of the lignocellulosic biomass to bioethanol contributes to the reduction of greenhouse gas emissions, enhancement of energy security, utilization of waste materials, and the promotion of sustainable agricultural practices. In this study, we report the effect of combining ball milling followed by liquid hot water (LHW) pretreatment of corn stover to lower the amount of enzyme required while also greatly increasing the recovery of xylose in fermentable form compared to either pretreatment alone. Short-duration ball milling for 60 min reduces the particle size of corn stover to 37.3 μm; however, the glucose only increased to 47% compared to 32% for unpretreated corn stover. In contrast, liquid hot water pretreatment alone can achieve increasing enzyme hydrolysis yields of cellulose from 49% to 93% as the pretreatment severity factor is increased from 3.24 to 4.41. However, the xylose yield decreased to 36% due to the fact that a considerable part of the xylose was degraded into furfural and humins. Surprisingly, the combination of mild ball milling (30 min) followed by mild liquid hot water pretreatment (190 °C, 15 min) could achieve both high glucose (83%) and xylose (72%) yields for a total sugar yield of 79%, theoretically. Thus, combining ball milling with liquid hot water pretreatment allows for milder conditions for both processes that lead to enhanced cellulose conversion without sacrificing xylose to degradation, which hinders enzymatic hydrolysis.