Robust high-performance hollow fiber membranes are needed for sour natural gas separation. In this study, a semirigid, cross-linkable, defect-free 6FDA-based polyimide hollow fiber membrane was developed and evaluated under pure H2S and three realistic sour natural gas feeds. No cross-linking-induced decline of H2S permeance was observed, indicating that the delicate asymmetric nanostructures of hollow fibers were well preserved during the cross-linking process due to the rigid molecular structure. For sour natural gas feed with low H2S concentration (0.5% H2S, 20% CO2, 79.5% CH4), the cross-linked hollow fiber membrane exhibited H2S permeance and H2S/CH4 permselectivity as high as 32 GPU and 30, respectively, at 450 psi and 35 degrees C. The CO2 permeance and CO2/CH4 permselectivity were also well maintained with values of 35 GPU and 32, respectively. Under more aggressive sour natural gas feeds (25% H2S, 5% CO2, 70% CH4 and 20% H2S, 20% CO2, 60% CH4), plasticization was observed for uncross-linked CF3 hollow fiber, but this phenomenon actually was beneficial for H2S separation. Specifically, H2S permeance and H2S/CH4 selectivity increased somewhat for the uncross-linked vs the cross-linked sample. In addition, the effects of sour gas composition on the performance of hollow fiber membranes were also considered. The results suggest increased H2S concentration in sour natural gas exhibits more pronounced effects on both H2S and CO2 permeance and selectivity than does increased CO2 concentration in the feed. Considering the impressive H2S and CO2 separation performance as well as the robustness of hollow fibers under highly aggressive sour natural gases, our work shows promising potential to simultaneously remove acid gases from sour natural gas with energy-efficient membrane processes under challenging feed conditions.