Phosphorylated cashew nut shell liquid prepolymer (PCNSL) was used as an organomodifier for kaolin and the role of the PCNSL-modified kaolin as a reinforcing nanofiller in natural rubber (NR) and its blends with polybutadiene rubber (BR) was studied. The organomodified kaolin was characterized using thermogravimetric analysis, powder X-ray diffraction, Fourier transform infrared spectroscopy (FTIR), high-resolution transmission electron microscopy and scanning electron microscopy. It was found that PCNSL could act as a coupling agent and compatibilizer between kaolin and rubber. Improved physico-mechanical properties were observed at a dosage of 6 phr of the modified kaolin in NR. Blends of NR with BR containing precipitated silica/PCNSL-modified kaolin hybrid filler showed improved tensile properties, tear strength and flex fatigue resistance along with lower heat build-up which could be beneficial for applications such as automobile tire sidewall.