The light-harvesting and energy diffusion process governing the light-to-chemical energy conversion applications of porous organic materials is subject to highly intensive researches showing the complex interplay between the photophysical properties of the framework and its topology . Among the different mechanisms, the Förster resonance energy transfer (FRET) mechanism is assumed to contribute as a main part of the process in most of the case. The Förster model establishes a relationship between the energy transfer rate kET and the absorption and emission spectra of the molecules, given by: Here, we assume that the CMP can be viewed as a sum of independent molecular units and, by using the photophysical parameters determined for the molecular model clusters, we applied the Förster model to estimate the rate of the energy transfer depending on the distance between the different pyrene chromophores and the Cp*Rh(Bpy) centers in Cp*Rh@PyrBpyCMP (see SI, Scheme 4). This basic analysis suggests that at the Rh:Bpy loading of 1:12 used in this work, the energy transfer can occur faster than 50 ps. This value is in good agreement with the quenching time determined by TCSPC measurements, and with the decay determined from the TAS measurements. It seems therefore reasonable to describe the photoactivation of the Rh metal center as an ultrafast transfer of excitation from a localized excited state of the Pyr2Bpy unit of the framework to a localized excited state of the [Pyr2Bpy]Cp*Rh metal centre forming of the active charge separated state between the pyrene and the Cp*Rh(Bpy) moiety as theoretically predicted . the MICT is rapidly converted ( < 1 ps) in a twisted intramolecular charge transfer (TICT) involving a charge separation between the pyrene and bipyridine moieties. The TICT is then converted within 10-100 ps into a LMCT species, corresponding to the activated form of the metal catalyst, with a ns lifetime. From the study in MeCN, ProCN and BuCN and in presence of TEOA, it appears that both the polarity and the viscosity of the reaction medium govern the formation of the LMCT state, suggesting that the degree of charge delocalization and probably also the torsional dynamics around the pyrenebipyridine bond are critical parameters in the photoactivation process. We performed the first femtosecond transient absorption measurements on the family of PyrBpy porous polymers from which we identified the formation of Pyr2Bpy-like MICT and TICT excited states upon the photoexcitation of the porous organic framework. We estimated from the time-resolved measurement and the FRET model, that these excited states can transfer the excitation to the catalytic metal center in less than 50 ps. Our results confirm the role of the Pyr2Bpy framework as light-harvesting macroligand for the Rh active site. More important, our results clearly demonstrate the complex role of the TEOA molecules that cannot be considered in the photocatalytic process only as passive sacrificial electron donors. Indeed, TEOA can also quench directly the excited state leading to reduce efficiency, and can also modulate the textural constraints of the flexible porous framework with consequences on the nature, i.e.TICT and/or MICT, and the lifetime of the excited states.