CMP are amorphous materials, made by covalent bonding between aromatic organic monomers, with large specific surface area and they can potentially exhibit electronic properties close to those of semiconducting materials. They can be furthermore combined with metal centres (M) dispersed through the porous framework to design photoactive catalysts. In order to conceptualize the mechanisms at play within these heterogenous materials as photocatalysts, two limiting cases have to be considered that are, on one side, the -conjugation is dominating and the photoactivation results from an interband optical transition generating an electron hole-pair (exciton) that diffuses quasifreely along the framework with stabilized electron (at, or close to, the metal centre) and hole (at the organic framework) and on the other side, the photoexcitation result in localized molecular excited states and activation proceeds by energy transfer (Förster, Dexter), and charge transfer, including the competition with the formation of exciplex species, as reported for MOFs. The photoinduced behaviour of M@CMP hybrids might be envisioned as a subtle mixture of these mechanisms, depending on the framework composition and metal binding, but also on the polymer topology (chain length and entanglement).