Thermal power plants are increasingly required to balance power grids by compensating for the intermittent electricity supply from renewable energy resources. As CO2 capture and storage is integrated with both coal- and gas-fired power plants, it is vital that the emission mitigation technology does not compromise their ability to provide this high-value service. Therefore, developing optimal process operation strategies is vital to maximise both the value provided by and the profitability of these important assets. In this work, we present models of coal- and gas-fired power plants, integrated with a post-combustion CO2 capture process using a 30 wt% monoethanolamine (MEA) solvent. With the aim to decoupling the power and capture plants in order to facilitate profit maximising behaviour, a multi-period dynamic optimisation problem was formulated and solved using these models. Four distinct scenarios were evaluated: load following, solvent storage, exhaust gas by-pass and variable solvent regeneration (VSR). It was found that for both coal- and gas-fired power plants, the VSR strategy is consistently the most profitable option. The performance of the exhaust by-pass scenario is a strong function of the carbon prices and is only selected at very low carbon prices. The viability of the solvent storage strategy was found to be a strong function of the capital cost associated with the solvent storage infrastructure. When the cost of the solvent tanks has been paid off, then the solvent storage scenario is 3.3% and 8% more profitable than the baseline for the pulverised coal and gas-fired power plants, respectively. Sensitivity analyses showed that, for all strategies, the flexibility benefit declined with reduced carbon and fuel prices, while a “peakier” electricity market, characteristic of one with significant quantities of intermittent renewables deployment, more significantly rewarded flexible operation.