A comprehensive investigation regarding the hygrothermal behavior of a constructive solution containing phase change materials (PCMs) was performed on a full-scale test cell, divided into two similar compartments. This involved hygrothermal monitoring (indoor air temperature) of the two compartments, in which one had PCM incorporated into the floor mortar. The main goal of this research was to investigate the potential of this kind of solution for overheating mitigation. The numerical study was conducted using EnergyPlus® software (version 9.0), exploring different natural ventilation flow rates to gauge the novel solution’s potential to reduce overheating rates. The results from the monitoring studies revealed prolonged periods of thermal discomfort in both test cells, particularly overheating. However, it was proven that the PCM application in one of the test cells led to a reduction of almost 10 °C in the maximum peak of air temperature. In the simulation analysis, the increase in the ventilation rate led to a linear decrease in the overheating hours of up to one renovation per hour, and then the reductions were attenuated.