The influence of molecular structure peculiarities on the supramolecular organization in the bulk and thin layers was studied by the example of two new meso-substituted ligands of tetraphenylporphyrin with substitution in alkoxygroups (-OC4H9) in para- or ortho-positions of phenyl rings. It is established that meso-alkyloxysubstituted tetraphenylporphyrin with substituents (-OC4H9) in the ortho-position (compound I) shows thermotropic monotropic mesomorphism, whereas the substitution in para-position (compound II) leads to the mesophase disappearance. The influence of substituent position on supramolecular organization of meso-substituted porphyrins in thin films was shown.