High molecular weight organic compounds are a class of pervasive materials at the borderline of molecular chemistry and materials science. Polymer synthesis, engineering and manufacturing have revolutionized the world of macromolecular chemistry at both academic and industrial basis. Among them, dendrimers are of particular interest owing to their structure reminiscent to natural trees and cells.1-2 Herein, the preparation of novel phosphorus-based architectures known as “onion peel” nanodendritic systems is reported. This construct is based on the versatility of synthetic methods and the capability of these systems to undergo regioselective reactions within the cascade structure.3 The “onion-peel” and classical dendritic units were fused within the same tectonic nanostructure by several polymeric condensation approaches including hydrazine-to-aldehyde Schiff-base formation and amine-to-carboxylic acid peptide-like coupling. These reticular, easy to run metal-free routes afford a new library of hyper-branched macromolecular materials featuring various phosphorus layers (both alternated and dissymmetrical), well-defined textured microspheres and controllable nanometric ordered substructures. The scope of the concept is successfully expanded to the integration of electro-redox viologen units resulting in the synthesis of novel photo-active macromolecular materials. 1- N. Katir, A. El Kadib, J. P. Majoral, A. M. Caminade, M. Bousmina, Eur. J. Org. Chem., 2012, 269-273 2- N. Katir, A. El Kadib, V. Collière, J. P. Majoral, M. Bousmina, Chem. Comm., 2014, 50, 6981-6983. 3- N. Katir, N. El Brahmi, A. El Kadib, S. Mignani, A. M. Caminade, M. Bousmina, J. P. Majoral, chem. eur. J., 2015, 21, 6400-6408.