Recently, the electrocatalytically active Rh complexes has been unveiled to be efficient in visible light assisted CO2 reduction in solution and heterogenized within MOF . Extending this strategy of single-site immobilization of the catalyst within a porous framework , the development of bipyridine-based porous organic polymers as platforms for the heterogenization of pentamethylcyclopentadienyl rhodium (Cp*Rh) catalytic species showing notably remarkable photocatalytic performances in the CO2 reduction to formic acid has been reported. In these photocatalysts, the pyrene-bipyridine (PyrBpy) or perylene-bipyridine (PerBpy) moieties constitutes a photosensitive conjugated macroligand that can absorb the photons below 450 nm. Time-resolved emission spectroscopy has revealed that in presence of Cp*Rh linked to the PyrBpy-CMP or PerBpy-CMP framework as porous macroligand, the excited state formed by photoexcitation at 400 nm is quenched within a few tens to hundreds of picoseconds featuring the ultrafast conversion between the excited stated state of the organic linkers to the activated metal centres. Quantum chemical calculations have been performed on a model [(5,5'-di(pyren-1-yl)-2,2'-bipyridine)(pentamethylcyclopentadienyl)rhodium] dichloride coordination complex, (hereafter Cp*Rh@Pyr2Bpy) and determined the ligand-to-metal charge transfer (LMCT) character of the exited state triggering the catalytic activity of the rhodium metal centre . The transient chemical species involved in the earliest stages of the CO2 photoreduction by Cp*Rh@Pyr2Bpy-CMP and Cp*Rh@Per2Bpy-CMP microporous polymers have not been so far experimentally characterized.