Corn is one of the major crops in most of the agricultural countries. In the US and China, the corn production shows increasing trends with the annual production of corn stover of 250 and 220 million tons respectively. Corn stover as an abundant renewable lignocellulosic biomass, has an excellent potential to be used for biofuel production. As it is resistant to physical and biological attacks due to the presence of lignin, it requires suitable pretreatment methods that can increase the yield of fermentable sugars after enzymatic saccharification. However, all types of processes used for pretreatment affect the total sugar yield before fermentation and result in the formation of inhibitory products. Thus, it is challenging to select the best pretreatment process. Therefore, researchers are more focused on identifying the best pretreatment method by combining two or more pretreatment techniques, which is convenient rather than a single pretreatment method to enhance the digestibility of maximum available sugars. In this review, detailed insight into the prospective and challenges of commonly used pretreatment techniques, particularly for corn stover as biomass, is presented to understand pretreatment's role in biofuel production. However, still there is a need for research to develop novel and more efficient pretreatment processes for the utilization of lignocellulosic biomass to produce useful products for conversion into biofuel.