A methodology for preparing porous epoxy monolith via chemically induced phase separation was proposed. The starting system was a mixture of an epoxy precursor, diglycidyl ether of bisphenol-A (DGEBA), a curing agent, 4,4'-diaminodiphenylmethane (DDM), and a thermoplastic polymer, polypropylene carbonate (PPC). As DGEBA was cured with DDM, the system became phase-separated having PPC particles dispersed in epoxy matrix. After PPC particles were removed by thermal degradation, a porous structure was obtained. The phase separation mechanism was determined by the initial composition and illustrated by a pseudophase diagram. The pore size increased with increasing the concentration of PPC and raising the curing temperature. The intermediate and final morphologies of the system were studied using optical and scanning electron microscopy, respectively. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 2140-2147, 2010