Energy retrofit solutions that concern a building’s roof structure play a significant role in the enhancement of a building’s thermal behaviour. This study investigates the integration of phase change materials (PCMs) with cool coatings (CCs) or thermochromic coatings (TCCs), namely, a PCM roof, a PCM-CC roof, and a PCM-TCC roof, as alternative and novel tactics for the simultaneous control of solar heat transfer and solar heat reflection. An energy simulation analysis with the DesignBuilder tool is conducted for a one-story residence and the climatic conditions of Athens. The simulation results indicate that, compared to the existing concrete roof construction, the PCM roof, PCM-CC, and PCM-TCC roof systems demonstrate energy savings that reach up to 13.55%, 16.04%, and 21.70%, respectively. The systematic analysis reveals that the increase in PCM’s thickness leads to an increase in the total electricity savings of the buildings, but in the case of PCM-CC and PCM-TCC roof systems, they merely effect the cooling thermal loads. The mean phase transition temperature that favours the cumulative electricity savings is 28 °C in the case of PCM and PCM-TCC roof systems and 35 °C in the case of PCM-CC roof systems. The methodology of this study allows the design of efficient, integrated roof systems with advanced thermal and optical properties as energy retrofit solutions for Mediterranean climatic conditions.