New polyimide (PI) nanocomposites containing two different amounts of MWCNT (PI/MWCNT) were prepared via in situ polymerization technique. Transmission electron microscopy showed that MWCNT was exfoliated in the polymer matrix, resulting in well-dispersed morphologies at 1 and 3 mass% MWCNT contents. The effects of multiwalled carbon nanotubes (MWCNT) on the thermal and flammability properties of new PI derived from 1,3-bis[4,4'-aminophenoxy]propane and biphenyl dianhydride were investigated by thermogravimetric analysis (TG) in nitrogen and air atmosphere, differential scanning calorimetry, and microscale combustion calorimeter (MCC). The PI/MWCNT nanocomposites were electrically conductive with maximum conductivity obtained at 3 mass% MWCNT, which is favorable for many potential applications. TG results showed that the addition of MWCNT resulted in a substantial increase of the thermal stability and char yields of the nanocomposites compared to those of the neat PI. Flame retardancy of the nanocomposites was significantly improved in the presence of MWCNT.