Hydrogen peroxide is a widely used and important chemical in industry. A two-electron electrochemical oxygen reduction reaction (2e– ORR) is a clean and on-site method for H2O2 production. Here, we report metal-free catalysts (mesoporous carbon hollow spheres, MCHS) for high-efficiency H2O2 production in neutral electrolytes (0.1 M PBS). The selectivity of H2O2 on MCHS catalysts is higher than 90% at a wide range of potentials (0.35–0.62 V), and it can reach 99.9% at a potential of 0.57 V. These catalysts show some of the best performances for H2O2 production in neutral electrolytes. It is preferable to develop H2O2 catalysts in a neutral environment, as the pH of the stabilizers used for H2O2 is also close to neutral. The outstanding activity of our catalyst comes from a combination of factors such as suitable porosity, the content of oxygen functional groups, and the types of different species of oxygen functional groups. First-principles simulations show that a catalyst with suitable mixed oxygen and COOH functional groups plays an important role in the catalytic formation of H2O2. The reported metal-free catalysts are promising catalysts for high-efficiency production of H2O2 in the future.

Bismuth (Bi) is a topological crystalline insulator (TCI), which has gapless topological surface states (TSSs) protected by a specific crystalline symmetry that strongly depends on the facet. Bi is also a promising electrochemical CO2 reduction reaction (ECO2RR) electrocatalyst for formate production. In this study, single‐crystalline Bi rhombic dodecahedrons (RDs) exposed with (104) and (110) facets are developed. The Bi RDs demonstrate a very low overpotential and high selectivity for formate production (Faradic efficiency >92.2%) in a wide partial current density range from 9.8 to 290.1 mA cm−2, leading to a remarkably high full‐cell energy efficiency (69.5%) for ECO2RR. The significantly reduced overpotential is caused by the enhanced *OCHO adsorption on the Bi RDs. The high selectivity of formate can be ascribed to the TSSs and the trivial surface states opening small gaps in the bulk gap on Bi RDs, which strengthens and stabilizes the preferentially adsorbed *OCHO and mitigates the competing adsorption of *H during ECO2RR. This study describes a promising application of Bi RDs for high‐rate formate production and high‐efficiency energy storage of intermittent renewable electricity. Optimizing the geometry of TCIs is also proposed as an effective strategy to tune the TSSs of topological catalysts.