A highly effective and facile synthesis route is developed to create and tailor metal‐decorated and nitrogen‐functionalized active microporous carbon materials from ZIF‐8. Clear metal‐ and pyrrolic‐N‐induced enhancements of the cyclic CO2 uptake capacities and binding energies are achieved, particularly at a much lower carbonization temperature of 700 °C than those often reported (1000 °C). The high‐temperature carbonization can enhance the porosity but only at the expense of considerable losses of sample yield and metal and N functional sites. The findings are comparatively discussed with carbons derived from metal–organic frameworks (MOFs) reported previously. Furthermore, the porosity of the MOF‐derived carbon is critically dependent on the structure of the precursor MOF and the crystal growth. The current strategy offers a new and effective route for the creation and tuning of highly active and functionalized carbon structures in high yields and with low energy consumption. Carbon control: A detailed structural analysis is performed for MOF‐derived nanoporous carbons, using ZIF‐8 as a case study as one of the most commonly used precursors. The controlled carbonization of ZIF‐8 yields very different porous carbons with variation of the activated C and N sites. The sample prepared at around 700 °C shows a high content of highly active N functional groups. The samples have enhanced CO2 uptake, binding, and selectivity due to the N and Zn sites.