Design, synthesis, general chemico-physical characterization, and study of the photophysical and photochemical properties of novel classes of mono- and multimetallic porphyrazine macrocycles, having innovative structural features, suitable for potential applications in the biochemical/biomedical field. Some of the studied porphyrazines are able to act as photosensitizers for the generation of singlet oxygen, the cytotoxic agent in photodynamic therapy (PDT) and may have potentialities to be used for a multimodal anticancer curative modality.