Abstract: Zeolite-templated carbons (ZTCs) have a unique three-dimensional (3D) ordered microporous structure and an extra-large surface area, and have excellent properties in adsorption and energy storage. Unfortunately, the lack of efficient synthesis strategies and the difficulty of doing this on a large-scale have seriously limited their development. We have developed a large-scale simple production route using a relatively low synthesis temperature and direct acetylene chemical vapor deposition (CVD) using Co ion-exchanged zeolite Y (CoY) as the template. The Co²⁺ confined in the zeolite acts as Lewis acid sites to catalyze the pyrolysis of acetylene through the d-π coordination effect, making carbon deposition occur selectively inside the zeolite at 400 °C rather than on the external surface. By systematically investigating the CVD temperature and time, the optimum conditions of 8 h deposition at 400 °C produces an excellent 3D ordered-microporous structure and outstanding structure parameters (3 000 m² g⁻¹, 1.33 cm³ g⁻¹). Its CO₂ adsorption capacity and selectivity are 2.78 mmol g⁻¹ (25 °C, 100 kPa) and 98, respectively. This simple CVD process allows the synthesis of high-quality ZTCs on a large scale at a low cost.