In low- and middle-income countries, electric motorcycles (EMs) are not generally well accepted in the community as many infrastructural, technological, and psychosocial barriers remain unaddressed. A greater understanding of adoption barriers perceived by motorcycle riders can help devise strategies, such as policy and behavioural change interventions, to increase the uptake of EMs. This study aimed to investigate the risk dimensions of EM adoption and integrate them into the Theory of Planned Behaviour to model users’ intention to adopt EMs. A multi-group analysis was also conducted to examine the moderating effect of demographic characteristics on the proposed model. The data were collected from two cities in Vietnam, making this one of the region's first theory-based studies on the electrification of the transport system. The outcomes of the structural equation modeling affirmed that the psychosocial variables outlined in the Theory of Planned Behaviour (i.e., attitudes, perceived behavioural control, and social norms) and perceived risk significantly influence the behavioural intention to adopt EMs. These findings hold significance for policymakers and manufacturers as they provide valuable insights into the factors that can be targeted to enhance the adoption of EMs. This represents a crucial step towards advancing sustainability goals in low- and middle-income countries.