Abstract. In the present study, silk was dissolved in CaCl 2 -formic acid and CaCl 2 -C 2 H 5 OH-H 2 O to obtain silk fibroin solution. The dissolve process, morphology, structure and mechanical properties of nanofibers prepared by electrospinning were studied. It showed that nanofibril structures were exhibited in the silk fibroin solution in CaCl 2 -formic acid compared with traditional method dissolving in CaCl 2 -C 2 H 5 OH-H 2 O solution, and the viscosity of the solution was much higher. The average diameter of nanofibers prepared by CaCl 2 -formic acid dissolution method was 375±26nm, and it showed well drawability, after stretching to 1 times, its breaking strength and elongation at break reaching 18.6±3.8MPa and 14.0±2.5%, respectively, was improved obviously relative to nanofibers prepared by CaCl 2 -C 2 H 5 OH-H 2 O dissolution method. It demonstrated that the good mechanical property of fibers was contributed to the fibrillar structures in the solution.