Tailpipe emissions from vehicles consist of CO2 and other greenhouse gases, which contribute immensely to the rise in global temperatures. Green hydrogen produced from the gasification of biomass can reduce the amount of CO2 emissions to zero. This study aims to provide a modelling framework to optimize the production of hydrogen from biomass waste obtained from different cities, for use in the road transport sector in Nigeria. A gasification model with post-treatment shift conversion and CO2 removal by adsorption is proposed. In this study, six cities are simulated based on technical and environmental considerations, using the Aspen Plus software package. The results revealed that Kaduna has the highest hydrogen generation potential of 0.148 million metric tons per year, which could reduce CO2 emissions to 1.60 and 1.524 million metric tons by the displacement of an equivalent volume of gasoline and diesel. This amounts to cost savings of NGN 116 and 161.8 billion for gasoline and diesel, respectively. In addition, the results of the sensitivity analysis revealed that the steam-to-biomass ratio and the temperature of gasification are positively correlated with the amount of avoided CO2 emissions, while the equivalence ratio shows a negative correlation.