The current communication present results from work on polymeric composites with extreme temperature performance. This study focuses on carbon fibre composites based on a new phenyl ethynyl terminated polyimide formulation NEXIMID® MHT-R (Nexam Chemicals AB, Sweden) based on hexafluoroisopropylidene bisphthalic dianhydride (6-FDA), 4-(Phenylethynyl)Phthalic Anhydride (4-PEPA) and ethynyl bis-phthalic anhydride (EBPA). In particular influence of post-cure conditions such as time, temperature and atmosphere on Tg of the composites is investigated. In addition to this monitoring and analyses of the consequences of post-cure on mass loss and occurrence of micro-cracks is carried out. Three different post-curing temperatures are considered in this study: 400°C, 420°C and 440°C. Two different atmospheres, air and inert by nitrogen, were also investigated. In summary the results reveal that remarkably high Tg, up to around 460°C, is achieved with only very limited mass loss. It was also observed that some, but limited amounts of, micro-cracks are developed within the laminates due to the inevitable high thermal stresses generated upon cooling from cure temperature.