This review presents an emerging biorefinery platform for C2-5 bioalcohol production through chemical synthesis using the organic waste materials. Bioalcohols are the most commercialized carbon-neutral transportation fuels, compatible with existing an internal combustion (IC) engine. However, current bioalcohol fermentation processes have made from sugar-rich edible crops. Also, carbon loss from the fermentation process is substantial. To minimize carbon loss, volatile fatty acids (VFAs) can be utilized as a raw material for bioalcohol production. Thus, a two-step chemical upgrading of VFAs into C2-5 alcohols is summarized in comparison with current challenges of biological fermentation processes for bioalcohol production. This review also provides the prospect of the hybrid biological/chemical process, presenting the technical advantages of the system. Finally, economic viability of hybridized process for bioalcohol production is compared with the current biological process.