In the field of construction, sustainable building materials are currently undergoing a process of technological development. This study aims to contribute to understanding the behavior of the fundamental properties of concretes prepared with recycled coarse aggregates that incorporate a polyethylene terephthalate (PET)-based additive in their matrix (produced by synthesis and glycolysis of recycled PET bottles) in an attempt to reduce their high porosity. Techniques to measure the gas adsorption, water porosity, Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) were used to evaluate the effect of the additive on the physical, mechanical and microstructural properties of these concretes. Porosity reductions of up to 30.60% are achieved with the addition of 1%, 3%, 4%, 5%, 7% and 9% of the additive, defining a new state in the behavioral model of the additive (the overdosage point) in the concrete matrix; in addition, the porous network of these concretes and their correlation with other physical and mechanical properties are also explained.