In this study, we present a novel, multifaceted pH-triggerable system of self-organized hierarchical nanostructures. The system consists of meso-tetrakis(4-sulfonatophenyl) porphyrin (TPPS) and poly(2-vinylpyridine) cylindrical brushes (PVP brushes) and can yield polymer-porphyrin networks, porphyrin loaded polymer brushes and pure porphyrin nanorods. In addition, the polymer influences the pK(a) and the mutual TPPS stacking geometry. Structures were characterized by AFM, dynamic light scattering using an IR laser, UV-Vis spectroscopy and small-angle neutron scattering (SANS). Supramolecular composite porphyrin structures that can be switched through external triggers have potential in photodynamic tumor therapy (PDT) and for nanoelectronics.