Synthesis of polypropylene/organo-layered double hydroxide (PP/OLDH) has been carried out based on selfassembled organocobalt aluminum LDH (0 CoAl LDH). The novel method of synthesizing sell-assembled CoAl LDH and its characterization have also been reported in details. This method is proven to be very efficient way of producing OLDH in a single step with homogeneous composition and structure. As flame-retardant nanofiller, 0 CoAl LDH shows significant decrease in heat release rate (FIR R), the total heat release (TH R) and the heat release capacity (1 RC) of the PP composites, though the thermal stability of the compounds decreases slightly compared to the base polymer. Morphological analyses show that the LDH particles are dispersed in PP matrix in a partially exfoliated form. The activation energy calculation based on the Kissinger method reveals that 0 CoAl LDH has a positive effect on the activation energy of thermal decomposition of PP. However, in the presence of this filler, decomposition of the composites starts at an earlier stage than that of pure PP.