In this work the phenomena involved with the microwave devulcanization of ground tyre rubber (GTR) were investigated. During studies three types of GTR characterized by different content of organic compounds (elastomers, plasticizers, etc..), carbon black and ash have been analyzed. The chemical structure of GTR before and after microwave devulcanization process was studied by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). Furthermore, efficiency of microwave devulcanization conducted at different time was evaluated based on the crosslinking density and sol content values. FTIR spectroscopy results shown that devulcanization of GTR causes a decrease in carbon black with generation of CO2 due to its thermo oxidation, a decrease in structural groups of elastomeric components (mainly methylene and methine) and a breaking of C-S groups and S-S bridges. The presented results indicate the strong correlation between content of SiO2 in GTR and its degree of devulcanization. It was observed that GTR with a high content of SiO2 are easier devulcanized than samples with low content of SiO2, which suggest the presence of silica fillers improve microwave devulcanization efficiency