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The study of structural masonry joined to geohydrological hazards in cultural heritage represents a multidisciplinary theme, which requires consideration of several aspects, among them the characterization of the materials used. In this paper, a first complete chemical, minero-petrographic, and physico-mechanical characterization of core samples taken from the masonry of two Florence riverbanks (<i>Lungarno degli Acciaiuoli</i> and <i>Lungarno delle Grazie</i>) is performed in order to identify the raw materials, technologies, and state of conservation and to support the planning of maintenance and restoration interventions. The physico-mechanical characterization of the riverbanks allows their stability to be determined. Such investigations allow identification of the level of compactness and cohesion of masonry; this information is useful for planning emergency interventions and for supporting planned restoration activities. The results provide valid support for the design of riverbank safety projects, to mitigate the risk of their collapse and to decrease the flood risk in the historic center of Florence.