Stony monuments have high artistic value and need continuously to be preserved from the damages of time, in particular from the detrimental effects of the weathering. One of the new environmentally-friendly (nano) materials for stone consolidation, particularly suitable for marble and calcareous (limestone, sandstone) artifacts, is Ca10(PO4)6(OH)2 hydroxyapatite (HAp), which shows a considerably lower dissolution rate and solubility compared to CaCO3 calcite, the building block of marble materials, especially in acidic environments, thus having been proposed for the protection of calcareous monuments against acidic rain corrosion. Promising results were obtained, but further optimization is necessary as the treated layer is often incomplete, cracked and/or porous. Many parameters have to be optimized to obtain a coherent and homogenous layer, and consequently to avoid the formation of metastable, soluble phases instead of HAp: the role of the pH of the starting solution; the effect of organic and inorganic additions, and in particular that of ethanol, that is reported to adsorb on calcite, hence possibly favoring the growth of the HAp layer. The formation of HAp nanoparticles and the applications on stony substrates were investigated by means of a multi-methodological approach, based on scanning electron microscopy, x-ray diffraction, small-and/or wide-angle x-ray scattering, Fourier-transform Infrared spectroscopy, completed by in situ measurements of laser-induced breakdown spectroscopy and acid attack preliminary test on stony substrates.