<p>One of the primary goals of the global economy is to develop economically effective, scalable, and sustainable technology for converting lignocellulosic biomass to liquid fuels. It is also a key component of a comprehensive plan to attain carbon neutrality. Herein we identify technology to achieve this promise by producing an alternative blendable fuel such as bioethanol from renewable carbon sources by chemocatalytic route which is carbon neutral and provides high atom economy. Moreover, based on the conversion technology and availability of feedstock, biofuels are categorized indicating that second-generation biofuels primarily from non-food crop residue containing cellulosic biomass is suitable to produce ethanol. The significance of hot water in cellulose hydrogenolysis is discussed and reveals that water is capable of self-ionization, due to which cellulose degradation and hydrolysis increase. Additionally, this review aims to provide a comprehensive picture of the chemocatalytic conversion of cellulose to ethanol by understanding the bond functionality for the series of cascade reactions including hydrolysis, retro aldol condensation, hydrogenolysis, and hydrogenation reactions. In this review, we discuss recent improvements in the chemocatalytic conversion of lignocellulosic biomass to ethanol, with an emphasis on analyzing the mechanisms of chemocatalytic routes. We believe that this review will provide fresh insight into the development of sustainable lignocellulosic biomass for direct ethanol synthesis.</p> Graphical Abstract <p></p>