Rural electrification with renewable energy technologies (RETs) offers several benefits to remote areas where diesel generation is unsuitable due to fuel supply constraints. Such benefits include environmental and social aspects, which are linked to energy access and poverty reduction in less-favored areas of developing countries. In this case, multi-objective methods are suitable tools for planning in rural areas. In this study, assessment of rural electrification with renewable energy systems is conducted by means of goal programming towards fuel substitution. The approach showed that, in the Non-Interconnected Zones of Colombia, substitution of traditional biomass with an electrification scheme using renewable energy sources provides significant environmental benefits, measured as land use and avoided emissions, as well as higher employment generation rates than diesel generation schemes. Nevertheless, fuel substitution is constrained by the elevated cost of electricity compared to traditional biomass, which raises households' energy expenditures between twofold to five times higher values. The present approach, yet wide in scope, is still limited for quantifying the impact of energy access improvements on poverty reduction, as well as for the assessment of energy system's technical feasibility.