In this work, the effect of the hydrophobicity of acrylic polymers on the membrane morphology was investigated. The membranes were prepared with poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA), poly (butyl methacrylate) (PBMA), poly(isobutyl methacrylate), and their blends using the wet phase inversion method. PMMA and PEMA having a relatively less hydrophobicity formed the channel-like structure, whereas PBMA and PIBMA having more hydrophobic units formed the finger-like structure. These morphological changes were attributed to differences in the solidification process of the polymer-rich phase determine d by the polymer/solvent/nonsolvent ternary phase diagram. The membrane structures of the blends were controlled by the main component of their blends.