The effect of isothermal ageing on two high temperature, bismaleimide composite materials, a novel CSIRO CBR 320/328 composite and a commercial CIBA GEIGY Matrimid® 5292 composite, was examined at 204 and 250 °C. Delamination is a major cause of failure in composite materials, therefore, the Mode I interlaminar fracture toughness (GIC) of both materials was measured using the double cantilever beam (DCB) test. Chemical degradation of the matrix was monitored concurrently using Fourier transform infrared (FTIR) and Raman spectroscopy. Chemical changes at the core of both of these materials were found to occur concomitantly with the observed changes in interlaminar fracture toughness. FTIR analysis of both matrix materials revealed the predominant degradation mechanism to be the oxidation of the methylene group bridging two aromatic rings common to the structure of both resins, and was substantiated by the ingrowth of a broad peak centred at 1600 cm−1 . In addition to this, the pyromellitic anhydride unit present only in the CBR 320/328 composites was found to be highly resistant to the effects of ageing, whereas the saturated imide, common to the cured structures of both materials, was observed to degrade. Raman spectroscopy indicated that the predominant degradation mechanism of the composites differed at the two ageing temperatures.