Thermally-isolating veneer ties and anchoring systems employing the same are disclosed. A ceramic based thermally-isolating coating is applied to the veneer tie, which is interconnected with a sheetmetal surface-mounted wall anchor. The thermally-isolating ceramic coating is selected from a distinct grouping of materials, that are applied using a specific variety of methods, in one or more layers and cured and cross-linked to provide high-strength adhesion. The ceramic coating maintains a thermal expansion similar to that of the underlying wire formative to prevent cracking. The thermally-coated veneer ties provide an in-cavity thermal break that severs the thermal threads running throughout the cavity wall structure, reducing the U- and K-values of the anchoring system by thermally-isolating the metal components.