In order to improve surface properties, high chromium austenitic base heat-resistant cast steel was scanned with a 5kW continuous wave CO2 laser, the specimen was aged at the temperature of 600°C~900°C. The microstructure and phase composition of the specimen were analysed with optical microscopy, electronic microscope and X-ray diffractionse. The hardness was measured. The results show that as-cast structure of high chromium cast steel is coarse and non-homogeneous, and mainly consist of austenite, ledeburite and carbides. After laser surface melting, the section is divided into the melted zone consisted of fine austenite and carbides, the heat affected zone composed of austenite and eutectic carbides, and the base meta1. The melted zone is very fine structures with dendritic crystals, only at the bottom a cellular structure is observed. A continuous carbide network is located in the austenitic grain boundaries at the heat affected zone. Carbides particles distribute dispersed out, the hardness of melted zone increases 35% than the base metal after aging. The area and the hardness of various zones are related to the laser processing parameters. The hardening depth of melted zone and heat affected zone may be up to 200μm~300μm.