The main features of high temperature chemical reactions under microwave (MW) heating have been considered. The efficiency of the MW power to heat conversion in a MW cavity is estimated, theoretically and experimentally, for different substances and conditions. The new approaches for MW processing of high-molecular hydrocarbons are proposed: (i) thermal decomposition in contact with microwave absorbing catalyst particles placed into liquid substrate; (ii) cracking of hydrocarbons pre-absorbed inside porous granules under rapid MW heating of adsorbent. It has been experimentally found that these approaches provide non-traditional conditions of reaction and can lead to the formation of valuable chemical products.