Ion attachment mass spectrometry was applied to evolved gas analysis-mass spectrometry (EGA-MS), generally known as thermogravimetry-mass spectrometry. Characteristic species arising from poly(vinyl alcohol) (PVA) and poly(methyl methacrylate) (PMMA) resin, used as a binder and a porogen, respectively, in the starting materials for porous ceramics, were detected in the mass spectra. The EGA curves of the characteristic mass peaks from PVA and PMMA, when plotted against the programmed temperature, successfully showed the individual pyrolysis behavior of each polymer during the firing process.