Pure alumina monoliths with well-defined macropores and mesostructured skeleton have been synthesized via a spontaneous route from the aqueous and ethanolic solution of aluminum salts in the presence of propylene oxide and high molecular weight poly(ethylene oxide)(PEO). The addition of propylene oxide to the starting solution controls the gelation, while the addition of PEO induces the phase separation. Appropriate choice of the starting composition, with which the phase separation and gelation concur, produces large-dimension (10mm×10mm×10mm), bicontinuous macroporous Al2O3 monoliths. The mean size of the continuously connected pores is controlled in the micrometer range, depending on the PEO concentration and polarity of the solution. On the other hand, micropores and mesopores, originated from the interstices among primary particles, exhibit median pore size of about 2.6 nm and the BET surface area as high as 396 m2/g after dried temperature at 40 °C.