Expanding renewable energy capacity in sub-Saharan transmission systems is a cornerstone of sustainable development, yet weak grid infrastructure and the absence of flexible storage remain principal barriers to reliable and low-carbon energy access. This paper addresses the economic and environmental dimensions of that challenge by proposing a hierarchical multi-objective framework for the optimal siting and sizing of Battery Energy Storage Systems (BESS), applied to the 130-bus Mali transmission network within the EMERGE project. The upper level employs the NSGA-II evolutionary algorithm to simultaneously maximize daily price-arbitrage revenue—the economic sustainability indicator—and minimize active power losses—the environmental efficiency indicator. For each candidate design, the lower level solves a multi-period DC Optimal Power Flow (DC-OPF) via CasADi/IPOPT, with thermal branch constraints embedded as hard linear inequalities through the Power Transfer Distribution Factor (PTDF) matrix, and voltage-corrected loss estimates recovered via a vectorized Extended DC Power Flow (EDCPF) model. Over 500 NSGA-II generations, the framework identifies Bus 91 (SIRAKORO II, 150 kV) as the dominant storage location, achieving maximum daily revenue of approximately € 10,033 at a marginal loss increment of 6.7×10−3 MWh. The Pareto front provides Mali system planners with a quantitative tool for balancing private investment returns against grid-level environmental impact, demonstrating that rigorous network-constrained BESS planning is both technically tractable and economically viable in the resource-constrained context of sub-Saharan sustainable energy transitions.