Electric cars (ECs) and electric motorcycles (EMs) can reduce the environmental load of transportation systems and boost energy security. To date, most studies have focused on ECs in industrialized economies. Less have considered barriers to electric mobility in developing countries, where motorcycles provide most transport. To contribute to this literature, this study aimed to systematically compare differences between barriers that impede EC and EM adoption. Focusing on Ho Chi Minh City, Vietnam, we leveraged data from a quantitative survey (n = 944) targeting potential adopters. Using exploratory factor analysis and a regression model, we investigated the influence of structural conditions—environmental, economic, social, institutional, etc.—on psychological factors that hamper EC/EM purchase intentions. Our findings reveal important commonalities and differences across barriers that hamper adoption intentions for each technology. This study thereby improves understanding of the complex interdependence among structural conditions in urban settings and their role in creating psychological barriers to electric mobility adoption.