An effect of nanosize CaCO3 on physical, mechanical, thermal and flame retarding properties of PBR was compared with commercial CaCO3 and fly ash filled PBR. CaCO3 at the rate of 9, 15, and 21 nm were added in polybutadiene rubber (PBR) at 4, 8 and 12 wt.% separately. Properties such as swelling index, specific gravity, tensile strength, Young's modulus, elongation at break, modulus at 300% elongation, glass transition temperature, decomposition temperature, flame retardency, hardness, and abrasion resistances were determined. The swelling index decreased and specific gravity increased with reduction in particle size of fillers in PBR composites. There was significant improvement in physical, mechanical, thermal and flame-retarding properties of PBR composites due to a reduction in the particle size of fillers. Maximum improvement in mechanical and flame retarding properties was observed at 8 wt.% of filler loading. This increment in properties was more pronounced in 9 nm size CaCO3. The results were not appreciable above 8 wt.% loading of nano fillers because of agglomeration of nanoparticles. In addition, an attempt was made to consider some thermodynamically aspects of resulting system. The cross-linkage density has been assessed by Flory-Rehner equation in which free energy was increased with increase in filler content.