Abstract: Silicalite-1 was synthesized by hydrothermal method. The catalytic performance of Silicalite-1 treated by different calcination temperatures in vapor phase Beckmann rearrangement of cyclohexanone oxime was investigated. Silicalite-1 catalysts were characterized by XRD, IR, BET and thermal analysis. The results show that the calcination temperature has an important effect on the conversion of cyclohexanone oxime and the stability of the Silicalite-1 catalyst, but no obvious influence on the selectivity of caprolactam. With the increase of calcination temperature, BET surface area of molecular sieve does not change significantly, while external surface area first increases and then decreases. The ratio of micropore volume to the total volume is on the decline. The Silicalite-1 calcinated at 400°C exhibits an excellent activity and stability in vapor phase Beckmann rearrangement reaction.