The transportation sector significantly influences an economy's development. The ongoing energy transitions and urgency to address an alternative to fossil fuels have simultaneously led to innovation-led growth. The stance of transport and research on sustainable mobility has become critical for ‘Smart Cities’. Climate change complexities put forward the need to adopt “Net-Zero” by 2050. Further, as the transport sector significantly contributes to total emissions, the ‘human–computer interaction’ aspect of Industry 5.0 can contribute to devising mitigation techniques, especially in the Global South. This chapter explores the infrastructural and technological barriers from a developed and developing nations context. Through the lens of alternative fuels such as electric vehicles, it critically evaluates the applications of Industry 4.0 in terms of cleaner technology and sustainable transport in smart cities through a comparative analysis and a detailed case study on sustainable transport. As Industry 5.0 entails intelligent machines coexisting with people, aiming for increased sustainability and resilience, it acts as a catalyst to the pre-existing pillars of Industry 4.0 to mitigate climate change. Hence, this chapter highlights the role of Industry 4.0 in the transport sector through the development of alternative fuel vehicles to aid in sustainable mobility solutions in Smart Cities.