The hollow fiber membranes spun with the approaching ratio α = 0.2 was found to have a high permeation flux and a large molecular weight cut-off (MWCO) due to the existence of water in the dope solution compared with those spun with the approaching ratio α = 0. The performance of the hollow fiber membranes was dominated by the shear rate of the dope solution within the spinneret according to shear induced molecular orientation. With an increase in shear rate, a low permeation flux and a small MWCO were achieved, and the pore size distribution curve of the membrane shifted to the left, indicating the membrane exhibited a good selectivity. The transition of the spinning process from the wet spinning to the dry-jet wet spinning strongly influenced the performance of the hollow fiber membranes, and a relative low permeation flux and a small MWCO could be obtained when the air gap was not less than 1 cm. With a decrease in the volume ratio of the dope solution to the bore fluid (ω), the membrane thickness became thinner, resulting in the increase of permeation flux and the MWCO.