Architectural expression and energy performance are key decision-drivers in the selection of a particular construction element, with the purpose of Urban Heat Island mitigation, energy-consumption reductions, and cultural heritage preservation in historical centers. In historical centers, the external layer of the envelope and the visible parts of the building are built with traditional materials and technological solutions, such as single-layer walls or brickworks, depending on the country's context, while the energy performance is usually optimized by means of internal insulation layers, or other active and passive solutions. Thermal-energy efficient materials and construction elements for the temperate, warm climate of the Mediterranean area are usually light-colored to reflect the largest part of solar radiation, thus reducing energy demands for cooling and improving thermal comfort conditions for occupants. On the other hand, many historical centers in such areas are characterized by reddish or grayish colors. In this work, we considered Italian historical areas, and other countries in the Mediterranean area with present similar situations. Thus, in this study, innovative, cool-colored, cement-based materials were developed to improve the thermal-energy performance of the external envelope of historical/historic built environments, without altering their appearance. These materials were prepared directly on-site, by mixing two types of pigments to achieve the desired color saturation. Optic and thermal properties were assessed, and yearly dynamic simulations of a historic, listed, case study building were performed, by comparing traditional-colored mortar and the prototype cool mortar envelopes. The research demonstrates that such cool-colored materials can maintain lower surface temperatures (−8 • C), while reducing energy demands for cooling (−3%).