A novel type of polyethersulfone porous microcapsule membranes with straight pores across the whole thickness was successfully prepared with a gel–sol phase inversion method for the immobilization of microbial cells. The mean diameter of the microcapsules was about 2 mm, and the microcapsule membranes were full of straight finger pores. The pore size distribution was from 3.5 to 53.6 μm and the median pore diameter was 13.6 μm. The prepared microcapsules had large total pore volume, and total pore area and porosity (as large as 91.7%). The prepared porous microcapsules were used as carriers for the immobilization of microbial cells in the anaerobic wastewater biotreatment process. Immobilized anaerobic microbial cells were found both inside the membrane pores and in the inner spaces of microcapsules. The prepared porous microcapsules were proven to be efficient for the microbial immobilization under anaerobic conditions.