Alternative renewable energy must emerge to sustainably meet the energy demands of the present and future. Current alternatives to fossil fuels are electricity from solar, wind and tidal energies and biofuels. Biofuels, especially bioethanol could be produced from lignocellulosic feedstock via pre-treatment and fermentation. The cellulose I content of most lignocellulosic feedstock is significant, yet its highly crystalline amphiphilic structure interlinked with the lignin network makes it difficult to process for bioethanol production. Processing lignocellulosic biomass via a range of physico-chemical, mechanical and biological pre-treatment methods have been well established, however a relatively new area on the use of cellulose II (a polymorph of native cellulose obtained via mercerisation or regeneration) for the production of bioethanol is still in its early stages. Hence, this review discusses in detail the advantages of using cellulose II over cellulose I as feedstock for bioethanol production. Furthermore, current green and sustainable methods for cellulose II production and the advantages and disadvantages of each method are discussed. In addition, examples from literature reporting higher fermentable sugar and bioethanol yields using cellulose II as feedstock are reviewed, thereby highlighting its importance in the field of bioethanol production. The conclusion from this review suggests that, in all the cases studied, fermentable sugar and/or bioethanol production was found to be higher when cellulose II was used as feedstock instead of native cellulose/lignocellulosic biomass. This higher yield could be attributed to the modified structural and lattice arrangement of cellulose II, its porous volume and degree of polymerisation.