Implementing a highly surface-dominated Na+ adsorption mechanism over carbon-based anodes is promising for high-rate and durable sodium storage. However, the nanostructure/microenvironment of most existing carbon materials still fails to sufficiently unlock the mechanism. Herein, we initially report selective deposition and confined pyrolysis strategies to engineer double-concave carbon nanorings (CNRs) with a precisely-controlled microenvironment to tackle this issue. The present strategies simultaneously endow the obtained CNRs with ultrahigh N-doping (N-CNRs, up to 18.6 at% even at 800 °C), rich defects, and thin-wall porous nanostructure. Such N-CNRs largely shorten the route distances for ion diffusion and provide enriched active sites, enabling highly surface-dominated sodium storage. Consequently, a high reversible capacity (387 mA h g−1 at 0.1 A g−1), outstanding rate capability (180 mA h g−1 even at 10.0 A g−1), with extra-long cycle life (over 10 000 cycles at 5.0 A g−1, 0.35 ‱ capacity decay per cycle) is achieved. In addition, the density functional theory calculations further illustrate that high N-doping carbon vacancy defects can effectively optimize electron density distribution, thereby significantly enhancing the capacity for sodium adsorption. This work opens a new avenue to microenvironment-engineered novel carbon nanostructures for highly surface-dominated sodium storage.