The aim is exploiting self-assembling of RGO platelets to provide a cost-effective method to tailor the dispersion of nanoparticles inside the host matrix, allowing to significantly decrease the percolation threshold for electric conductivity and drastically change the dependence of gas barrier on nanofiller concentration. Self-assembling of reduced graphene oxide (RGO) platelets (‘segregated’ arrangement), as a tailored interconnected network within natural rubber and butyl rubber matrices, is proposed as a mean for obtaining nanocomposites with significantly enhanced functional properties as compared to unloaded rubber, i.e. gas barrier properties and electric conductivity, even at very low filler contents. Interestingly, the prescribed spatial arrangement of the nanoparticles results to be much more effective in improving properties than homogeneous dispersion (‘not segregated’ arrangement) of platelets, even at low loadings. The ‘segregated’ structure originates from the confinement of platelets within the interstices of the coagulated latex particles, which act as a template for the network formation. The platelets are assembled on the latex particles giving rise to spheres with a core-shell structure, with a partial or complete covering depending on graphene amount. Conversely, the ‘not-segregated’ structure is obtained by destroying this interconnected network by further processing the RGO nanocomposite masterbatch via twin-roll mixing, thus determining a uniform orientation of exfoliated RGO platelets.