The structure and performance changes of aromatic copolysulfonamide (co-PSA) fibers that occurred during wet spinning process have been studied. While using different length scale characterization, including scan electron microscopy (SEM), wide-angle X-ray scattering (WAXS), and small-angle X-ray scattering (SAXS), it was found that the molecular chains of co-PSA formed an isotropic network during coagulation which further lead to extension and orientation of these chains during the subsequent stretching. As a result, only after heat stretching and heat setting the molecular chains tended to pack into crystal lattice in the fibrils. This gave rise to a much denser structure along the spinning line and the glass transition temperature of co-PSA fibers increased a little after heat setting. Before heat stretching, the co-PSA fibers were in amorphous state, and only the amorphous orientation was observed within the fibers. After heat stretching at the temperature higher than T g , the fraction of amorphous region decreased, and the crystal structure formed in the fibers, which became more perfect during heat setting. The structure development during spinning process contributed toward the improvement of thermo-mechanical stability, tenacity and modulus of the co-PSA fibers. V C 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42343.