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In the current paper, the effect on Indoor Air Quality (IAQ) of two commercial acrylic-based paints were compared: one (Paint A) for indoor applications, the other (Paint B) for indoor/outdoor applications. Both were applied on an inert and on a real mortar substrate. The possibility of Paint B to passively improve IAQ was also investigated when adding highly porous adsorbent fillers, both as addition or as total replacement of a conventional siliceous one. The obtained results show that all paints have high capacity to inhibit biological growth. Paint A is more breathable and it has a higher moisture buffering capacity. Paint B negatively modifies the beneficial properties of the mortar substrate for IAQ. However, the use of unconventional fillers, especially as addition to the formulation, allows the recovery of the same properties of the substrate or even the enhancement of about 20% of the ability to adsorb volatile organic compounds (VOCs) under the current test conditions.