We present a geographic information system (GIS)-based tool for estimating the performance of photovoltaic (PV) mini-grid system over large geographical areas. The methodology consists of geospatial analysis and mapping of the energy output and reliability of PV mini-grid system. The algorithm uses a combination of hourly solar radiation data from satellites combined with measured data on PV module and battery performance and estimated electricity consumption data. The methods also make it possible to optimize the PV array and battery storage size for a given location. Results are presented for an area covering Africa and most of Southern and Central Asia. We also investigate the effects of using Li-ion batteries instead of the traditional lead-acid batteries. The use of our spatial analysis as decision support tool could help governments, local authorities and non-governmental organizations to investigate the suitability of PV mini-grids for electrification of regions where access to electricity is lacking. In this way it is possible to identify areas where PV mini-grids are most suitable.