The relationship between solar photovoltaic (PV) rural electrification and energy-poverty was assessed using social, economic and environmental indicator-based questionnaires in 96 solar-electrified and 113 non-electrified households in rural Ghana. The purpose was to assess the energy-poverty status of households with and without solar PV systems, and to determine the factors that explain energy-poverty in off-grid rural households. Principal component analysis (PCA) was used to construct energy-poverty index scores (EPISs). On the basis of the results of the EPISs, about 80% of the non-electrified households were assessed as relatively energy-poor compared with only 10% of the solar-electrified households. Three significant indicators increased linearly with increasing energy-poverty index score (EPIS) and therefore explained the variation in EPIS. They are monthly savings on lighting (r2 = 0.214), number of children who can sit around lighting (r2 = 0.388) and amount paid to obtain lighting/electricity system (r2 = 0.261). On the contrary, EPIS decreased linearly with increasing monthly costs of kerosene, candles and dry-cell batteries. This indicates that increasing expenditure on kerosene, candles and dry-cell batteries is likely to affect household savings and investment in quality energy delivery systems that can increase EPIS. To improve EPIS, households should invest a bit more in reliable and quality energy delivery systems, which can help to improve their quality of life. The use of EPISs successfully demonstrated the difference in energy-poverty status between households with and without solar PV. This lays down a basis of understanding the relationship between solar PV rural electrification and energy-poverty improvement in off-grid communities.