Polyamic acid(PAA)/organoclay nanocomposites containing phosphorous were prepared by solution blending of phosphorylated PAA(PPAA) and organically modified montmorillonite(O-MMT) as a type of layered clays. The nanocomposites were characterized by FT-IR, DSC, TGA, PCFC, SEM, and XRD. The preparation of nanocomposites was confirmed by FT-IR and XRD. SEM pictures showed that the organoclay was dispersed well in the PAA matrix relatively. XRD results indicated that the O-MMT layers were intercalated. The thermal stability and flame retardancy of O-MMT/PPAA nanocomposites were higher than those of pure PAA. PCFC results also showed that the heat release capacity and total heat release values of O-MMT 4 wt%/PPAA-0.2, 0.4, 0.6 composites were decreased with increasing the mole ratio of phosphorous. It was found that the nanocomposite films had the potential to be used as a fire safe material.