Anthropogenic carbon dioxide (CO2) emissions are a major contributor to rising global temperatures. Adsorbing CO2 inside porous materials is one way to reduce atmospheric CO2 levels. Metal organic frameworks (MOFs) are promising porous materials for the adsorption of CO2. Here, we report the study of a luminescent MOF (LMOFs), so-called LMOF-202. We have employed Grand Canonical Monte Carlo (GCMC) simulations to understand and explain the adsorption phenomena inside LMOF-202, and, on the basis of these insights, we have varied the metal ions in LMOF-202 to increase the CO2 affinity and selectivity of the material. We show that the CO2 adsorption capacity and selectivity can be increased by approximately 1.5 times at 1 bar and 298 K by changing the metal ion from Zn to In. We also report the feasibility of using this material to capture CO2 from flue gas under realistic conditions (1 bar and 298 K). This work shows that LMOF-202 merits further consideration as a carbon capture adsorbent.