Data available indicate that the use of solar PV systems in off-grid rural communities is plagued with barriers, which must be carefully researched. Without a clear quantification of impacts, potential users may not accept solar PV as an appropriate alternative for electricity generation. Using with/without comparison technique, 209 households and 47 micro-enterprises with and without solar PV systems were surveyed in rural Ghana. Principal component analysis was used to construct energy-poverty index scores (EPIS), descriptive statistics was used to analyse the impacts and Pareto analysis was used to identify priority areas and barriers that need to be removed. From the results, about 80% of the non-electrified households were assessed as relatively energy poor compared with only 10% of the solar-electrified households. The use of solar PV lighting reduced the proportion of household members being affected by indoor smoke from kerosene lanterns by 50%. The priority factors that can increase the future use of rural solar PV systems are low pricing of parts, availability of parts on the local market, low monthly fees, and access to end-user financing.