This study investigates the potential of different stages of the bioethanol production process (pretreatment, hydrolysis, and distillation) for bioethanol and biomethane production, and studies the critical steps for the liquid and the solid fractions to be separated and discarded to improve the efficiency of the production chain. For this, Napier grass (a fast-growing grass) from Effurun town of Delta State in Nigeria was used and the novel pretreatment method, nitrogen explosive decompression (NED), was applied at different temperatures. The results show that the lowest glucose (13.7 g/L) and ethanol titers (8.4 g/L) were gained at 150 • C. The highest glucose recovery (31.3 g/L) was obtained at 200 • C and the maximum ethanol production (10.3 g/L) at 170 • C. Methane yields are higher in samples pretreated at lower temperatures. The maximum methane yields were reported in samples from the solid fraction of post-pretreatment (pretreated at 150 • C, 1.13 mol CH4/100 g) and solid fraction of the post-hydrolysis stage (pretreated at 150 • C, 1.00 mol CH4/100 g). The lowest biomethane production was noted in samples from the liquid fraction of post-pretreatment broth (between 0.14 mol CH4/100 g and 0.24 mol CH4/100 g). From the process point of view, samples from liquid fraction of post-pretreatment broth should be separated and discarded from the bioethanol production process, since they do not add value to the production chain. The results suggest that bioethanol and biomethane concentrations are influenced by the pretreatment temperature. Napier grass has potential for bioethanol and further biomethane production and it can be used as an alternative source of energy for the transportation sector in Nigeria and other countries rich in grasses and provide energy security to their population.alternative sources of energy that will decrease the share of fossil fuels utilised in the transportation sector and productive uses, reduce environmental concerns caused by the extensive utilization of these resources (e.g., climate change and global warming), increase energy security, and improve the access of the population to electricity. Renewable energy sources from lignocellulosic biomass have been reported as promising solutions to these problems [4]. Nowadays, biomass itself is responsible for 10% primary energy consumption worldwide [5] and it can be used as a promising feedstock for biofuel production. The sustainability of wastes and by-products as a biofuel for the transportation sector in a circular economy has been studied in the literature, in order to make the biogas-biomethane chain more sustainable [6][7][8]. These studies show the positive impact of biofuels in the transportation section in Europe. However, further research needs to be done in order to apply circular economy models to emerging economies.Sub-Saharan Africa has great potential to develop renewable energy sources, such as wind, biomass, solar, and hydro. Just in Nigeria, the biomass potential is about 144 million tonnes per year and the potenti...