This work attempts to show the usefulness of vibrational spectroscopy (i.e., FTIR and Raman) in the analysis of major components of the original structure materials of a heritage monument (Tropaeum Traiani, Adamclisi). The features of materials and indoor microclimatic variables (i.e., temperature and relative humidity), on the periods of the monitoring campaigns, were considered. As the conservation must make sure about the physicochemical and structural aspects of the materials, assessment of the environmental impact, deterioration processes and characterization of ancient building materials are useful to understand the chemical evolution in the past, predict the various trends in the future, choose the suitable restoration methods to preserve their present state, and even to describe the alteration process of materials and modification through time. The surface of original structure materials used until present seems not to be affected at major scale by the indoor microclimate variables. But even high recorded relative humidity levels promote the occurrence of amorphous calcium carbonate, calcite, aragonite and vaterite highlighted by vibrational spectroscopy data (i.e., FTIR and Raman), as a first effect, the development of biological organism can be enhanced, depending on the characteristics of the substrate. Second, atmospheric pollutants can be dissolved easier in the humidity existing in the porous material, and lastly, if the waterflow inside the stone is not homogeneous, cracks could appear due to differences in permeability.