This review describes the authors work on coordination of azaferrocene (AF) to metalloporphyrins metallophthalocyanines and photochemistry of these macrocyclic complexes in the presence of AF. It has been found that AF is a very efficient electron donor towards photoexcited macrocyclic complexes enabling their facile photoreduction. The high photosensitivity of the system metal macrocycle – AF allowed e.g. reversible photoejection of dioxygen from its _η1-complexes with Co(II) porphyrins and photoreduction of methylviologen sensitized by metallophthalocyanines in homogenous water solutions.