Gothic arch calcite, a specific crystallographic variety of calcite known from some hot springs and tufa streams, has been newly recognized in the Koněprusy Caves. The gothic-arch calcite occurs on the exteriors of exotic coralloid speleothems where it coexists with scalenohedral (dogtooth) spar crystals. The crystals exhibit microscopic ultrastructural features including deeply eroded topography, etch pits, and spiky and ribbon calcite crystallites, pointing to its extensive natural etching. Many gothic-arch calcites originated as late-stage, secondary overgrowths on older, etched dogtooth calcite crystals. Its characteristic outward curvature resulted from the recrystallization of etching-liberated fine carbonate grains and newly formed needle-fiber calcite laths, which were accumulated and bound on the faces and at the bases of corroded crystals. These intimately coexisting destructive and constructive processes of carbonate crystal corrosion and growth were probably mediated by bacteria, fungi, or other microorganisms. Fluid inclusions embedded in calcite crystals point to a vadose setting and temperatures below ~50 °C. This, combined with the wider geological context, indicates that the gothic arch calcite crystals originated only during the late Pleistocene to Holocene epochs, when the cave, initially eroded by hypogene fluids in the deeper subsurface, was uplifted to the subaerial setting and exposed to the meteoric waters seeping from the topographic surface. The radiocarbon analysis shows that gothic-arch calcite crystals are generally older than ~55,000 years, but the surface layers of some crystals still reveal a weak 14C activity, suggesting that microbiologically mediated alterations of the speleothems may have been occurring locally until now.