Solid sorbents are essential for developing technologies that directly capture CO2 from air. In solid sorbents, metal oxides and/or alkali metal carbonates such as potassium carbonate (K2CO3) are promising active components owing to their high thermal stability, low cost, and ability to chemisorb the CO2 present at low concentrations in air. However, this chemisorption process is likely limited by internal diffusion of CO2 into the bulk of K2CO3. Therefore, the size of the K2CO3 particles is expected to be an important factor in determining the kinetics of the sorption process during CO2 capture. To date, the effects of particle size on supported K2CO3 sorbents are unknown mainly because particle sizes cannot be unambiguously determined. Here, we show that by using a series of techniques, the size of supported K2CO3 particles can be established. We prepared size-tuned carbon-supported K2CO3 particles by tuning the K2CO3 loading. We further used melting point depression of K2CO3 particles to collectively estimate the average K2CO3 particle sizes. Using these obtained average particle sizes, we show that the particle size critically affects the efficiency of the sorbent in CO2 capture from air and directly affects the kinetics of CO2 sorption as well as the energy input needed for the desorption step. By evaluating the mechanisms involved in the diffusion of CO2 and H2O into K2CO3 particles, we relate the microscopic characteristics of sorbents to their macroscopic performance, which is of interest for industrial-scale CO2 capture from air.