The aim of our present study was the development of a drug multilayer-based carrier system for delivery of water-insoluble drugs. As drug, we applied the anticancer drug 5,10,15,20-tetrakis(3-hydroxyphenyl)porphyrin, mTHPP, which is a model photosensitizer for photodynamic therapy. Gold nanoparticles (AuNP) with a diameter of 14.5 ± 0.9 nm were prepared and used as template for the layer-by-layer approach. The drug and the negatively charged polyelectrolyte (PE) poly(styrene sulfonate) sodium salt (PSS) were complexed with a new developed method using freeze-drying. The complexation efficiency was determined to be ∼11-12 monomers PSS per mTHPP molecule by CHNS analysis and UV/vis measurement. Molecular docking simulations revealed π-π interactions and H-bonding to be the responsible mechanisms. A drug multilayer system based on the layer-by-layer (LbL) technique utilized the water-soluble complex as anionic layer material and poly(allylamine hydrochloride) (PAH) as cationic layer. The modified AuNP were characterized by different physicochemical techniques such as UV/vis, ζ-potential, ICP-OES, and TEM. To the best of our knowledge, we could demonstrate for the first time the adsorption of three drug layers to a nanoparticulate system. Furthermore, the adaptation of the LbL-technique resulted in drastically increased drug deposition efficiency (factor of 100). Furthermore, we developed a new and comfortable way to solubilize water-insoluble drugs in water.