Cross-linked microporous carbon beads (MCBs) were successfully synthesized via a green, convenient, and cost-efficient strategy derived from a renewable sugar source. Such an approach avoids the time-consuming procedure and the use of corrosive chemical activating agents and toxic solvents and only involves a simple carbonization process, which makes it to be applicable for rapid and large-scale industrial production of MCB materials. The obtained MCBs possessed well-defined microporous structure, narrow pore size, and high surface area. Particularly, the microporosity of the resultant MCBs could be easily tailored to arise primary pores of size 0.5–0.9 nm by adjusting the carbonization temperature and reaction time, which remarkably favor the CO2 capture. The optimal sample of MCBs-9-5 carbonized at 900 °C for 5 h was characterized by high microporosity (80% of the surface area from micropores), especially ultrahigh narrow microporosity (53% of pore volume from micropores of size <1 nm), which endowed it a great satisfactory CO2 uptake of 4.25 mmol g–1 at 25 °C and 1 bar. Significantly, a prominent CO2/N2 selectivity and superior recyclability of MCBs-9-5 were also achieved. Combined with the simple fabrication, the satisfactory adsorption capacity, and high selectivity, MCBs-9-5 should be a promising adsorbent for CO2 capture and separation.