Vulcanized graphene/natural rubber composites with a conductive segregated network exhibiting good electrical conductivity, water vapor permeability and high mechanical strength are prepared by self-assembly in latex and static hot pressing. The composite exhibits a percolation threshold of ∼0.62 vol% and a conductivity of 0.03 S m⁻¹ at a content of 1.78 vol%, which is ∼5 orders of magnitude higher than that of the composites made by conventional methods at the same loading fraction.