This paper presents a complementarity-driven optimization framework for the integration of battery energy storage systems (BESS) in the Brazilian National Interconnected System (SIN). The proposed approach combines large-scale spatiotemporal analysis of renewable resources with a detailed Mixed-Integer Linear Programming (MILP) model to evaluate the operational benefits of complementarity between hydropower, wind, and solar generation. Spatial complementarity is assessed using long-term historical datasets from the NASA POWER database, enabling the identification of regions with strong temporal anti-correlation between natural resources. These complementarity indicators are incorporated into the optimization model through a novel economic weighting mechanism applied to renewable curtailment penalties. The optimization framework is implemented in Python using Pyomo and solved with the Gurobi Optimizer, representing hydroelectric dynamics, thermal unit commitment, transmission constraints, and battery storage operation. Three scenarios are evaluated: a baseline case, a complementarity-only case, and a full flexibility case including BESS. The results demonstrate that complementarity alone reduces renewable curtailment, while the integration of storage leads to an almost complete elimination of curtailment and significantly improves system flexibility. Additionally, the model reveals important interactions between renewable resources, hydropower operation, and storage systems, highlighting the role of complementarity as a structural driver of system efficiency. The proposed framework provides a consistent methodology for integrating resource complementarity into operational planning, contributing to the development of more reliable and flexible renewable-dominated power systems.