Reconfigurable electronic states in insulating materials enable metal-like transport while preserving the intrinsic robustness and functional versatility of insulating hosts, thereby redefining materials beyond the conventional metal-insulator dichotomy. However, obtaining such states remains extremely challenging owing to strong electronic localization inherent in insulating materials. We demonstrate a universal surface single-atom engineering strategy for linear and deep programming of electronic transport in insulating oxides and nitrides, including SiO2, Al2O3, and BN, by selectively inducing local symmetry breaking, effective bandgap compression, and impurity-band percolation. Consequently, this strategy continuously narrows the bandgap and ultimately yields metallic transport characteristics with anomalously minimal temperature dependence. Furthermore, we apply single-atom-anchored SiO2, an intrinsically electromagnetic wave-transparent material, to shielding with a record-high effectiveness of 98.6% for an ultrathin 80 µm film that also maintains stable performance over a temperature range of 300-800 K. This counterintuitive performance defies the conventional paradigm, demonstrating that an intrinsically insulating material can achieve electromagnetic shielding comparable to state-of-the-art metals while avoiding the temperature-induced performance degradation of metallic shielding materials. Overall, we believe that this study establishes single-atom band engineering as a general strategy for programming electronic transport in insulating materials, with broad implications for advanced electronics and unconventional functionalities.
Keywords: electromagnetic shielding; electronic transport; insulating material; metal–insulator dichotomy; single‐atom band engineering.
© 2026 Wiley‐VCH GmbH.