Ultrafiltration hollow-fiber membranes (UHFMs) of poly(acrylonitrile-co-maleic acid) (PANCMA) were prepared by a dry-wet phase inversion process. The morphologies of inner surface and cross section for these hollow fibers were inspected with scanning electron microscopy. It was found that, by increasing the amount of solvent DMSO in internal coagulant, the number and size of macrovoid underneath the inner surface decreased. The water flux of the UHFMs also decreased while the bovine serum albumin rejection increased minutely. These results were interpreted based on the ternary phase diagrams for the PANCMA/DMSO/(H2O+DMSO) system, which was obtained from the experimental cloud point measurements and empirical linearized cloud point relation. It was envisaged that the membrane surface could be further modified by the reaction of acid groups with poly(ethylene glycol).