The control of the transmission of the energy transported by optical waves is of extreme importance for the realization of those advanced technologies which require high speed of operation and fast switching. Such a task can be approached through the design and preparation of materials that possess modulable optical properties. In the present review the aspect of material science behind the realization of the effect of optical limiting, OL (or optical power limiting, OPL), will be considered focusing on those materials based on conjugated metallo-macrocycles like porphyrins, phthalocyanines and derivatives. The choice of these molecular materials for OL purposes is motivated by the fact that the optical properties of such annulated systems can be finely modulated in a controlled fashion by changing the chemical structure of the complex. These changes involve the variation of the central metal, the extent of electronic conjugation of the ring, the nature and the number of peripheral ligands, and the eventual introduction of axial ligands coordinated by a central metals with a valence higher than +2. An attempt will be made to establish relationships between the structure of the macrocyclic complex and the relative OL properties taking into account the most recent developments in the field. During this analysis we will also discuss the aspect of optically passivity, i.e. the characteristic of the OL materials of undergoing fast changes of optical properties according to an internal mechanism of self-activation.