The growing share of variable renewable energy sources in power systems is increasing the need for short-term operational flexibility—particularly from large industrial electricity consumers. This study proposes a practical, two-stage optimization framework to unlock this flexibility in cement manufacturing and support participation in electricity balancing markets. In Stage 1, a mixed-integer linear programming model minimizes electricity procurement costs by optimally scheduling the raw milling subsystem, subject to technical and operational constraints. In Stage 2, a flexibility assessment model identifies and evaluates profitable deviations from this baseline, targeting participation in Spain’s manual Frequency Restoration Reserve market. The methodology is validated through a real-world case study at a Spanish cement plant, incorporating photovoltaic (PV) generation and battery energy storage systems (BESS). The results show that flexibility services can yield monthly revenues of up to €800, with limited disruption to production processes. Additionally, combined PV + BESS configurations achieve electricity cost reductions and investment paybacks as short as six years. The proposed framework offers a replicable pathway for integrating demand-side flexibility into energy-intensive industries—enhancing grid resilience, economic performance, and decarbonization efforts.