The work aims to prepare ceramic coating via laser pyrolysis of polydimethylsiloxane (PDMS). The PDMS solution was uniformly coated on clean steel substrate and cured at constant temperature to obtain uniform organic coating. Then the organic coating was scanned with CO2 continuous laser to fabricate ceramic coating after pyrolysis. Composition and structure of the product obtained by laser pyrolysis of PDMS were analyzed, and effects of such laser parameters including laser power, laser scanning times and scanning linear velocity on ceramization of PDMS were studied by using scanned electron microscopy (SEM), X-ray diffractometer (XRD) and X-ray photoelectron spectroscopy (XPS). Lower laser power (eg. 700 W), fewer scanning times (eg. 1 time) and higher scanning linear velocity (eg. 18 mm/s) would lead to more evident layer-mesostructure, more cracks and larger pores of the coating surface. In contrast, higher laser power (eg. 1000 W), more scanning times (eg. 3 times) and lower scanning linear velocity (eg. 10 mm/s) were conductive to remove the layer-mesostructure, and the coating surface tended to be more refined and flat. The laser power, laser scanning times and scanning linear velocity have great influence on ceramization degree of polydimethylsiloxane, and formation and phase transition of crystalline β-SiC. High laser energy provides enables the polydimethylsiloxane to absorb more laser energy, hence leading to more thorough ceramization of PDMS, nevertheless it may cause the phase transition of crystalline β-SiC into amorphous α-SiC, which is not conducive to the formation of crystalline β-SiC.