Porous Al₂O₃ membranes were prepared through a phase-inversion tape casting/sintering method. The alumina membranes were embedded with finger-like pores perpendicular to the membrane surface. Bare alumina membranes are naturally hydrophilic and underwater oleophobic, while fluoroalkylsilane (FAS)-grafted membranes are hydrophobic and oleophilic. The coupling of FAS molecules on alumina surfaces was confirmed by Thermogravimetric Analysis and X-ray Photoelectron Spectroscopy measurements. The hydrophobic membranes exhibited desired thermal stability and were super durable when exposed to air. Both membranes can be used for gravity-driven oil/water separation, which is highly cost-effective. The as-calculated separation efficiency (R) was above 99% for the FAS-grafted alumina membrane. Due to the excellent oil/water separation performance and good chemical stability, the porous ceramic membranes display potential for practical applications.