A metal organic framework (MOF) based on the Cu4I4DABCO2 cluster (DABCO = 1,4‐diazabicyclo2.2.2octane), MOF 1, shows bright emission with a maximum at 556 nm and an emission quantum yield of 0.53 in the solid state. When the large cavities of the MOF are loaded during the synthesis with different amounts of ferrocene {FeCp2, (η5‐C5H5)2FeII}, the luminescence of MOF 1 decreases with the increase in the ferrocene content, reaching an almost complete quenching for 3.5 wt.‐% of cage loading, corresponding to the complete filling of the MOF cavities. When an electric potential is applied to the FeCp2@MOF 1 deposited onto an ITO glass, the FeIICp2 is oxidised to FeIIICp2+, and the MOF 1 emission is partially switched on again, indicating that a photoinduced electron‐transfer reaction is contributing to the quenching process. MOF 1 is made of nodes based on luminescent Cu4I4 cubane clusters and saturated amines as bridging ligands, and it is loaded with FeCp2 (η5‐C5H5)2FeII molecules, which quench the luminescence. When FeCp2 is oxidised to FeIIICp2+ the emission is partially switched on again.