To study the influence of structure peculiarities of porphyrin derivatives on their supramolecular organization in thin films, 15 new mesa-substituted tetraphenylporphyrin derivatives and their metal complexes with substituents (-OC4H9 or -OC16H33) in para or ortho positions were studied. The films of the studied compounds were obtained by the Langmuir-Schaefer method. The behavior of porphyrin derivatives at the water-air interface was analyzed, and the conformity of the influence of molecular structure on supramolecular organization in floating layers and Langmuir-Blodgett films was defined. The absorption of these films over a wide spectral range was analyzed. The supramolecular organization of mesa-substituted tetraphenylporphyrin derivatives was modeled and specified with the help of X-ray diffraction analysis. It was determined that the formation of monomolecular layers is typical for the compounds with short lateral substituents or without substituents. Tetraphenylporphyrins with extensive substituents can form a monolayer only when zinc is included in the molecular structure.