In this paper the provision of flexible generation is investigated by extracting steam from Rankine-cycle power stations during off-peak demand in order to charge thermal tanks that contain suitable phase-change materials (PCMs); at a later time when this is required and/or is economically effective, these thermal energy storage (TES) tanks can act as the heat sources of secondary thermal power plants in order to generate power, for example as evaporators of, e.g., organic Rankine cycle (ORC) plants that are suitable for power generation at reduced temperatures and smaller scales. This type of solution offers greater flexibility than TES-only technologies that store thermal energy and release it back to the base power station, since it allows both derating but also over-generation compared to the base power-station capacity. The solution is applied in a case study of a 50-MW rated oil-fired power station unit at the autonomous system of Crete. The optimal operation of the TES system is investigated, by solving a modified Unit Commitment – Economic Dispatch optimization problem, which includes the TES operating constraints. The results indicate that for most of the scenarios the discounted payback period is lower than 12 years, while in few cases the payback period is 5 years.