A macrovoid structure was found in polysulfone membranes formed by the wet-inversion method using N-methylpyrrolidinone (NMP) and water as the solvent/nonsolvent pair. The addition of Span series surfactants in the casting solution was found to inhibit the macrovoid formation. Sorbitan monooleate (Span-80) was more effective in inhibiting macrovoids than was sorbitan monolaurate (Span-20). The phenomenon of macrovoid suppression became more prominent at higher temperature. The cloud-point shift might account for the temperature effect. But there was no simple explanation for the effect caused by Span-80. The cloud-point position, the demixing rate, and the viscosity of the casting solution were measured. None of them could explain the effect of macrovoid inhibition by the addition of Span-80. However, the penetration test indicated that the penetration of a nonsolvent into a surfactant-free casting solution was caused by a convective flow, but that into Span-80 was through diffusion. It was found that the retardation of nonsolvent penetration was the major cause of macrovoid inhibition.