In response to the increasing penetration of volatile and uncertain renewable energy, the regional transmission organizations (RTOs) have been recently focusing on enhancing the models of pump storage hydropower (PSH) plants, which are one of the key flexibility assets in the day-ahead (DA) and real-time (RT) markets, to further boost their flexibility provision potentials. Inspired by the recent research works that explored the potential benefits of excluding PSHs ’ cost-related terms from the objective functions of the DA market clearing model, this paper completes a rolling RT market scheme that is compatible with the DA market. Then, with the vision that PSHs could be permitted to submit state-of-charge (SOC) headrooms in the DA market and to release them in the RT market, this paper uncovers that PSHs could increase the total revenues from the two markets by optimizing their SOC headrooms, assisted by the proposed tri-level optimal SOC headroom model. Specifically, in the proposed tri-level model, the middle and lower levels respectively mimic the DA and RT scheduling processes of PSHs, and the upper level determines the optimal headrooms to be submitted to the RTO for maximizing the total revenue from the two markets. Numerical case studies quantify the profitability of the optimal SOC headroom submissions as well as the associated financial risks.