TiO2 is employed as both photocatalytic and structural materials, leading to its applications in external coatings or in interior furnishing devices, including cement mortar, tiles, floorings, and glass supports. The authors have already demonstrated the efficiency of photoactive micro-sized TiO2 and here its industrial use is reported using the digital printing to coat porcelain grés slabs. Many advantages are immediately evident, namely rapid and precise deposition, no waste of raw materials, thus positively affecting the economy of the process. Data for the thin films deposited by digital printing were compared with those obtained for the conventional spray method. The use of metal-doped TiO2 is also reported so that the photoactivity of these materials can be exploited even under LED light. The digital inkjet printed coatings exhibited superior photocatalytic performance owing to both higher exposed surface area and greater volume of deposited anatase, as well as the greater areal distribution density of thinly and thickly coated regions. Moreover, the presence of TiO2 doped silver increased the efficiency of the materials in NOx degradation both under UVA and LED lights.