Abstract The present study is dealing with the obtaining of transparent hybrid silica materials encapsulating 5,10,15,20-tetrakis(3,4-dimethoxyphenyl)-21H,23H-porphyrin designated for advanced optoelectronic devices. The porphyrin was synthesized by three methods: an Adler-type reaction between pyrrole and 3,4-dimethoxybenzaldehyde in propionic acid medium; by Lindsey condensation of pyrrole with 3,4-dimethoxybenzaldehyde in the presence of BF 3·OEt 2 and by a multicomponent reaction by simultaneously using of pyrrole and two different aldehydes: 3,4-dimethoxybenzaldehyde and 3-hydroxybenzaldehyde. The 3,4-dimethoxyphenyl substituted porphyrin was characterized by HPLC, TLC, UV–vis, FT-IR, 1H NMR and 13C NMR analysis. Excitation and emission spectra were also discussed in terms of pH conditions. The hybrid materials, consisting in the porphyrin encapsulated in silica matrices, have been prepared successfully via the two steps acid–base catalyzed hydrolysis and condensation of tetraethylorthosilicate using different approaches of the sol–gel process: in situ, by impregnation and by sonication. The synthetic conditions and the compositions were monitored and characterized by using spectroscopic methods such as FT-IR, fluorescence and UV–vis. Atomic force microscopy (AFM) has been applied to observe the columnar or pyramidal nanostructures which are formed by the immobilization of porphyrin on the silica matrices.