In order to avoid both natural and artificial stone decay, mainly due to the interaction with atmospheric pollutants (both gases such as NOx and SO2 and particulate matter), polymeric materials have been widely studied as protective coatings enable to limit the penetration of fluids into the bulk material. In the current work, an air hardening calcic lime mortar (ALM) and a natural hydraulic lime mortar (HLM) were used as substrates, and commercially available Si-based resins (Alpha®SI30 and Silres®BS16) were adopted as protective agents to give hydrophobicity features to the artificial stones. Surface properties of coatings and their performance as hydrophobic agents were studied using different techniques such as contact angle measurements, capillary absorption test, mercury intrusion porosimetry, surface free energy, colorimetric measurements and water vapour permeability tests. Finally, some exposure tests to UV radiation and to real polluted atmospheric environments (a city centre and an urban background site) were carried out during a wintertime period (when the concentrations of the main atmospheric pollutants are higher) in order to study the durability of the coating systems applied. The effectiveness of the two commercial resins in reducing salt formation (sulphate and nitrate), induced by the interaction of the mortars with the atmospheric pollutants, was demonstrated in the case of the HLM mortar. Graphical Abstract ᅟ.