Silk fibroin hydrogels is an important morphous of biomaterial. As a natural protein collosol, purified native silk fibroin solution can be gelatinized under certain conditions. The main mechanism of the gelation is that the fibroin molecules turn into the β-sheet conformation from the random coils. This transformation of silk fibroin molecules would be influenced by various parameters such as the temperature, pH value, ion concentration and so on. In this paper, the effect of ultrasonication on the gelation velocity and structure of silk fibroin were discussed. It is believed that the cavitations caused by sonication could accelerate the process of gelation of silk fibroin. Our experiments demonstrated that the ultrasonic treatment could greatly reduce the silk fibroin gelation time, especially at a high sonication power exceeding 400W. The results of XRD, FTIR, and Raman spectra indicated that the ultrasonication had no significant effect on the final structure and composition of the silk fibroin gels except the acceleration for the molecular transition from random coil and α-structure to β-sheet conformation of silk fibroin. The SEM images showed freeze-dried fibroin gels close to the ultrasonication source had compact structure, while the structure was more loosening far away to the source.