In this paper, we report the synthesis of hybrid silver nanostructures (AgNPs) based on an effective mixing of polyols with Polyvinylpyrrolidone (PVP) and Porphyrin molecules, in particular Protoporphyrin IX (PP). The combination of PVP and PP, which act as co-directing agents and favour the anisotropic growth of nanostructures, yields to very stable complexes for six months. The resulting hybrid silver nanoparticles have been further characterized by polarization modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS), UV–Visible spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM), revealing that the main role of Porphyrin molecules in the formation of silver nanostructures.