Changes of the water content in drawn silk during drying were investigated by thermal analysis and H-1 pulse NMR. Water in liquid silk by drawing extruded from the inside of the silk filament into ambient air. The water contents in the drawn silk decreased with drying time. Assuming the nonfreezing water has a concentration of 10 wt % in the liquid silk, the percentage distribution of water in liquid silk is composed of 10 wt % nonfreezing water, 40 wt % freezing water, and 30 wt % free water. This 40 wt % freezing water in the liquid silk may be important for the formation of fine pores on the surface of drawn silk. The apparent pore radius, which was calculated from the results of thermal analysis, on the surface of drawn silk decreased to 5.0 nm and finally to 2.0 nm. The calculated apparent fine pore formed on the surface by drawing was 4.0 nm.