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Polyimide nanocomposites were prepared with 0 and 1 wt% single wall-and double wall- CNTs (functionalized and non-functionalized) from BPADA and BAPP by refluxing in NMP. These nanocomposites were characterized using FT-IR, TGA, DSC, tensile strength, and Positron annihilation lifetime spectroscopy (PALS). The FT-IR spectra for all the samples showed the characteristic peaks of polyimide. TGA curves showed weight loss with temperature in two stages. The first stage 180-300 °C showed a weight loss of ~ 15% that may be associated with the release of trapped NMP. The second stage 500-750 °C with a drastic weight loss is associated with decomposition. The residual weight is ~ 40% at 750 °C for both pure polyimide and polyimide nano composites made with functionalized single or double wall CNTs. The non-functionalized CNT dispersed polyimide showed similar two-step behavior, but the weight loss is remarkably less and about 80% weight remained at 750 °C. DSC curves of all polyimide samples showed two distinguishable endothermic peaks at around 90 °C (the onset of NMP release) and 200 °C (structural change). PALS was used to study the nano-porosity. Positron lifetime has a correlation with tensile strength showing a decrease in tensile strength with increasing pore size in CNT-polyimide composites.