Recently, near-ultraviolet (NUV)-emitting quantum dots (QDs) have attracted considerable attention for their potential in next-generation NUV-driven white-lightemitting diodes (with color rendering index >90). However, their widespread application in lighting products is greatly hindered by the inferior NUV-emitting efficiency, poor temperature stability, and toxicity of currently available Cd-/ Pb-containing QD systems. In the present work, we report the synthesis of ecofriendly Al 2 O 3 -surrounded (AS)-ZnO QDs using a novel technique based on atomic layer deposition, which shows a superior quantum yield (QY) of 97.3% in the NUV band (395 nm), in contrast to <63% in literature results. Furthermore, the AS-ZnO QDs possess extraordinary thermal stability, which demonstrates little efficiency degradation or structure deterioration above room temperature, retaining a QY of 87% at 500 K. The high-efficient and thermally stable NUV emission is revealed to originate from the surface states of ZnO QDs, instead of the intrinsic emission. Under an ultrastrong quantum confinement effect, the energetic level of surface states in AS-ZnO QDs is highly enhanced from 2.1 eV to 3.14 eV (with reference to the valence band), close to the intrinsic bandgap of ZnO, and the ratio of radiative to nonradiative recombination on the surface states from ∼5% to above 97%, making them very efficient NUV emitters. The underlying mechanism has been discussed in detail. The outstanding optical merits, combined with facile synthesis and nontoxicity, promise AS-ZnO QDs great potential in lighting applications.