Over the past decades, climate change has been the subject of serious international negotiations. Solar photovoltaic (PV) energy has caught the eyes of many governments as one of the front-runner technologies for the low-carbon energy transition in the global community. However, over 1.3 billion people in the world still have no access to electricity. In this regard, this article sets out to examine opportunities of PV electrification using off-grid PV systems coupled with Li-ion batteries in less developed and developing countries. The main objectives of the study are to define to what extent solar PV power is an energy option that can be considered more secure, affordable and environmentally-friendly compared with the most likely competing technology (diesel generators) in these regions. However, the added value of article is placed to include the interests of PV market development in new regions from the position of developed countries. The study is based on data of 49 countries from energy poverty regions with good solar resources. The sample represents 1.06 billion people with no access to electricity. The proposed opportunities can solve several global sources of anxiety with a more sustainable and affordable energy supply system. Furthermore, it is in the interest of developed countries to develop new markets in pursuit of new growth engines. This can lead to new outlets to resolve the global PV overcapacity issues. The enhanced competitiveness of PV power benefiting from the enlarged market size and experience would eventually contribute to future national installations in developed countries with reduced PV costs. As a result, a ‘virtuous circle’ could be created in the PV sector on a global scale. Therefore, global collaborative actions that widen the energy security frontier based on abundant PV resources are highly recommended for not only environmental sustainability, but also global economic benefits.