Bioethanol, a sustainable energy solution derived from renewable biomass, has gained prominence, with corn stover emerging as a substantial biomass resource in Indonesia. Corn stover, a corn residue, is one of the top three agricultural wastes worldwide and is abundantly available. However, a significant portion of corn stover is burned in fields rather than utilized for bioethanol production, whereas it has potential as a bioethanol feedstock. As the world strives to realize sustainable and environmentally friendly energy security, bioethanol production from corn stover can be one of the solutions to be developed. Nonetheless, the current immaturity of bioethanol production technology is one of the causes of large‐scale production failure. The present paper comprehensively reviews the technological aspects and process optimization of bioethanol production using corn stover as a feedstock comprising pretreatment, hydrolysis, fermentation, and bioethanol purification processes. According to our critical review, ammonia fiber expansion (AFEX) pretreatment is the most effective conventional pretreatment, with glucose yield up to 90%. Moreover, ultrasound appears to be the most viable option for nonconventional pretreatment of corn stover for producing bioethanol. However, combining ultrasound pretreatment and dilute aqueous ammonia produced 80.6% sugar output. Furthermore, enzymatic hydrolysis emerges as the most effective saccharification, yielding up to 81.39%. Moreover, the fermentation process of corn stover with the saccharification and co‐fermentation (SScF) method and the process optimization with response surface methodology (RSM) could produce bioethanol with a concentration of up to 59.8 g/L and 92.07% ethanol yield, respectively. This review also reveals that pervaporation for the purification process is the best choice for producing bioethanol with high purity up to > 99%. In addition, this method could reduce the energy used by 6.6% lower, 24.2% lower carbon footprint, and have the lowest total capital and production costs compared to conventional molecular sieves and extractive distillation. We believe this review article can provide a reference for selecting the best bioethanol production process from corn stover for further research.