The surface temperature of casting slab is an important parameter in the metallurgy field. Because the surface emissivity is uncertain and also unknown, it is difficult to measure the slab surface temperature accurately. A method based on preceded reflector and multi-wavelength was put forward to deal with the difficulty in surface temperature measurement of casting slab. On the premise of preceded reflector and non-preceded reflector, the method establishes the radiation energy equations and works out the emissivity and temperature in the equations. Also, the multilayer modeling of casting slab surface and multiple reflection-absorption process modeling were built by Monte Carlo method. The temperature measuring method had been applied in the continuous casting field. In order to verify the measured result, the thermal imaging method was adopted when the slab surface emissivity was set by repeated tests. Finally, the measured and verified temperature curves keep a same tendency and the error of the values is lower than 5℃. The comparison result shows that the method can measure temperature accurately.