Many developing countries are at a crucial juncture in road transport electrification with electric mobility because they have limited economic capacity to implement government policy support and financial mechanisms that have spurred the capital-intensive electric mobility growth in developed countries. Attracting private sector investments remains a viable option for developing countries. While investors have identified opportunities to invest in developing countries, it remains to be seen which countries to prioritise, considering the complexities involved in investment decision-making despite the availability of myriad investment appraisal tools. This paper contributes to this academic and policy debate. With a power and transport sector coupling viewpoint, we explain the interaction of the power and transport sectors in the context of decarbonisation and digitalisation to identify developing countries that could be considered for private sector investment in electric mobility. Then, we apply our framework to case studies of the Philippines, Argentina, Romania, and Poland. We argue that countries with wholesale power markets and wholesale and retail power markets could attract electric mobility investment. We offer policy recommendations for stakeholders interested in electric mobility investment issues in developing countries.