The stone Ensemble from Corbii de Piatrǎ Romania arouses a continuous scientific interest, with the final goal being to obtain an exhaustive and multidisciplinary package of results that will become the support of an extensive restoration project. The cave painting stands out as the most important and most affected by the advanced degradation among the historical monuments in Romania. This article provides for the first time a radiocarbon dating of the first forms of painting by establishing the age of the mortar/plaster used as a pictorial support. Being a very complex context from the point of view of the type of datable material and the disappearance over time through degradation of other elements that would ensure a simpler and more reliable radiocarbon dating (such as the straws used to form the material), it was necessary to use a multidisciplinary approach for the selection of samples and for supporting the radiocarbon results. The set of analyses consisted of visualization techniques through microscopy and compositional analysis, providing information on the similarities/differences between the samples, the degradation mechanisms/impurities and the quality of the calcium carbonate dated by the Accelerator Mass Spectrometry (AMS) technique. The results supported each other, ensured the selection of reliable radiocarbon data and established the most probable moment of the early interventions, namely the two phases corresponding to the 14th century.