Metal nodes and organic ligands are important structural units of MOFs, and their properties can profoundly affect the photocatalytic activity. Herein, two ferrocene-based MOFs with FeO6 or AlO6 clusters as the metal nodes and 1,1′-ferrocenedicarboxylic acid (H2FcDC) as the ligands were successfully synthesized. Comparing with normal organic ligands, ferrocene ligands have longer-lived photogenerated charges due to metal-to-ligand charge transfer (MLCT) process, leading to a better photocatalytic activity of the corresponding ferrocene-based MOFs. In addition, the FeO6 clusters are able to further accept the photogenerated electrons from ferrocene ligands compared to the inert AlO6 clusters, allowing a long-distance charge transfer process, namely the proposed metal-to-ligand-to-metal charge transfer (MLMCT) process, which results in a better performance towards photocatalytic CO2 cycloaddition reaction. This work sheds a light on designing MOFs using ferrocene ligands with high photocatalytic activity.