This paper examines the greyish-blue deposits that were recently discovered in the lower levels of the Sima de la Higuera Cave (Murcia, SE Spain) which occur as patinas over the walls and ceilings, as well as coating boxwork formations. Their mineralogy was determined using XRD and micro-Raman spectroscopy, while EDX microanalysis was used to determine their elemental composition. The mineralogical analyses revealed the presence of Mn oxides (todorokite and pyrolusite) and Fe with a low degree of crystallinity, whereas EDX microprobe showed elevated concentrations of Mn (38.2 wt.%), Fe (15.2 wt.%) and Pb (8.1 wt.%). The ferromanganese oxyhydroxides occur as botryoidal aggregates overlying blades of calcite that have a visibly sugary texture. The speleogenetic model proposed describes (1) an initial phase of precipitation of hydrothermal calcite veins (of hypogenic origin) within the fissures of the host rock under phreatic conditions and (2) a subsequent vadose phase involving preferential corrosion of the carbonate host rock caused by lowering of the pH resulting from CO2 diffusion in condensed water and oxidation of Fe and Mn under aerobic conditions, probably mediated by microorganisms. It is this later phase that gave rise to the boxwork. The boxwork of the Sima de la Higuera Cave is a singular example of a formation that is generated by dissolution–corrosion of the rock due to acidification caused by oxidation of iron and manganese.