The facile latex approach has been adopted to finely incorporate graphite nanosheets into elastomeric polymer matrix to obtain high-performance elastomeric nanocomposites with improved mechanical properties and functional properties. Scanning electron microscopy, transmission electron microscopy and X-ray diffraction experiments show that the nanostructures of the final nanocomposites exhibit a high degree of exfoliation and intercalation of graphite in the nitrile-butadiene rubber (NBR) matrix. Mechanical and dynamic-mechanical tests demonstrate that the NBR/graphite nanocomposites possess greatly increased elastic modulus and tensile strength, and desirably strong interfaces. The unexpected self-crosslinking of elastomer/graphite nanocomposites was discovered and then verified by oscillating disc rheometry and equilibrium swelling experiments. After critically examining various polymer types by X-ray photoelectron spectroscopy, electron spin resonance and Fourier transform infrared spectroscopy, a radical initiation mechanism was proposed to explain the self-crosslinking reaction. These NBR/graphite nanocomposites possess significantly improved wear resistance and gas barrier properties, and superior electrical/thermal conductivity. Such versatile functional properties make NBR nanocomposites a promising new class of advanced materials.