The palace of Nuevo Baztán is a state-designated historic monument in central Spain built in the early eighteenth century. The main building material used in its facades is limestone. The aim of this investigation was to characterize the limestone, defining deterioration mechanisms contributing to the decay of the stone facades and testing a series of potential preservation treatments. The limestone is a biosparite; two microfacies were identified according to microscopic differences (limestones A and B) with distinct petrophysical characteristics mainly due to their different pore systems. Primary deterioration mechanisms were identified as those related to cycles of thermal and hygric stress, biodeterioration and those associated with structural movements. Main decay forms in the surface of the stone are erosion with material loss, spalling and flaking, chromatic alteration, fissures and biodeterioration. Conservation products possessing water-repellent properties were therefore considered. From an initial selection of ten products, two siloxane-based products were ultimately determined to be the most effective on the basis of chromatic variables, water vapour permeability, water-stone contact angle, scanning electron microscope observations and durability (artificial ageing tests). Both products reduce water absorption rates and are expected to slow the rate of limestone decay. This study also demonstrates the value of advance testing of potential treatment methods before application in the field.