The major aim of this study is to propose an economic chemical plant for conversion of biomasses into biofuels within CO2 capture which can make a big contribution to the energy demand and environmental protection. Therefore, a novel process for conversion of rice straw using sorption enhanced biomass chemical looping gasification (SE-BCLG) to butanol and pentanol is simulated in Aspen Plus V 8.8. In this regard, the wet rice straw is turned into the syngas after drying and SE-BCLG stages. Then, the butanol and pentanol are produced after acid gas removal, alcohol production and purification sections. In addition, an optimization and a techno-economic assessment are carried out to evaluate the process. The technological analysis shows that the process can produce 222.6 t.day−1 butanol and pentanol from 960 t.day−1 rice straw. The economic analysis illustrates that the total investment to start the project and the total annual operating cost of the process are MUS$ 642.707 and 43.965 MUS$.year−1, respectively. Finally, it is proved that the butanol production cost for the proposed plant is 1286.532 US$.t−1. Therefore, these results indicate that the proposed process if this study is more economic than some other studies.