Utilizing SHS Reactive Flame Spraying (RFS) technology, TiC-TiB2-Al2O3 multiphase ceramics coatings were produced on steel substrate. Phase constituents and microstructure of the ceramic coatings were analyzed. The procedure of chemical combustion and structure transformation, reactive mechanism, and solidifying behavior during spaying were emphasized. Reactants which influenced on SHS spraying was discussed. SHS reactive spraying processes were studied. Mechanical properties of the coatings were tested. Utilizing SHS Reactive Flame Spraying (RFS) technology, TiC-TiB2-Al2O3 multiphase coatings coatings were produced on steel substrates. Phase procedure and microstructure of the ceramic coatings were analyzed. The procedure of chemical combustion and structure transformation, reactive mechanism, and solidifying behavior during spaying were emphasized. Reactants which influenced on SHS spraying was discussed. SHS reactive spraying processes were studied. Mechanical properties of the coatings were tested.