Regenerated silk fibroin (SF) filaments were prepared by the wet spinning technique. The effect of coagulation conditions, such as coagulant type and coagulation temperature, was investigated on the morphological feature of SF filaments and a theoretical approach was also performed to understand the coagulation phenomena. SEM observation revealed that as the R group size of alcoholic coagulant (ROH) increased, the cross-sectional shape deviated more from a circular form. This is attributed to the fact that as the R group size increased, the mass transfer rate difference increased, but the coagulation rate decreased due to a reduced diffusion rate. Most non-alcoholic coagulants exhibited this circular cross-sectional shape, except dioxane, which showed a clover shape. As the coagulation bath temperature increased, the cross-section deviated less from a circular form, with the reduction of fiber diameter. When methanol/water mixture was used as a coagulant, an ellipse or a dog-bone shape was obtained with higher water content in methanol, which was attributed to the decrease of coagulation rate. Although methanol exhibited a positive value of mass transfer rate difference, a circular shape of cross-section was obtained due to the density difference of the coagulated and uncoagulated parts in the coagulating SF filament.