This study is addressed at the cultural heritage of the UNESCO historical centre of Urbino (Italy) through the focus on a very peculiar building and ornamental carbonate porous (spongy) stone also found in the opus quadratum Roman dry walls. For these rocks, the mathematician and historian Bernardino Baldi (16th century AD) and the mineralogist Francesco Rodolico (middle of the 20th century AD) introduced, respectively, the popular terms of Tufo spugnoso or Pietra Spugna. Physical observations and stable isotope data (δ13C and δ18O) of these rocks allowed, for the first time, their classification as calcareous tufas, thus contributing to the valorization of the stone heritage of the city. This carbonate lithotype was formed by the chemical precipitation of CaCO3, driven by the CO2 degassing of supersaturated calcium-bicarbonate-rich waters, coupled with the passive encrustations of organic material in continental environments. Radiocarbon analyses dated these stones mostly between 9100 and 4700 yr. BP when a maximum growth of these carbonate continental deposits occurred in Mediterranean regions and northern Europe, i.e., during the Holocene Atlantic climatic optimum. Work is still in progress on a perched springline of calcareous tufas found along the Metauro Valley (a few km from Urbino), being good candidates for provenance, at least for those blocks exploited by the Romans and successively reused in the architectural framework of Urbino.