In the contemporary era, conventional energy sources like oil, coal, and natural gas overwhelmingly contribute 89.6% to global CO₂ emissions, intensifying environmental challenges. Recognizing the urgency of addressing climate concerns, a pivotal shift towards renewable energy, encompassing solar, wind, and biofuels, is crucial for bolstering environmental sustainability. Bioethanol, a globally predominant biofuel, offers a versatile solution, replacing gasoline or integrating into gasoline–ethanol blends while serving as a fundamental building block for various valuable compounds. This review investigates the dynamic landscape of biomass generations, drawing insightful comparisons between the first, second, third, and fourth generations. Amid the drive for sustainability, the deliberate focus on the initial generation of biomass, particularly corn, in bioethanol production is grounded in the current dependence on edible crops. The established utilization of first-generation biomass, exemplified by corn, underscores the necessity for a comprehensive examination of its advantages and challenges, allowing for a nuanced exploration of existing infrastructure and practices. To produce bioethanol from corn feedstock, various milling methods can be employed. Thus, this paper delves into a comparative assessment of dry-milling and wet-milling processes scrutinizing their efficiency, environmental impact, and economic feasibility.