Aluminum hydroxide covered multiwalled carbon nanotubes (A-MWCNTs) were synthesized as a conducting additive to alumina-epoxy-terminated poly(dimethylsiloxane). The measured diffusivity and calculated conductivity exhibited dissimilar behavior between several Al2O3 concentrations as a function of A-MWCNT loading, which correlated with the interface density and interconnectivity of the structures. The fabricated heterostructured A-MWCNT did not have a significant effect on the thermal conductivity of the composite because of phonon scattering at the interface. A small amount of A-MWCNT was feasible for establishment of a heat conductive percolating network with the greatest enhancement of thermal conductivity and diffusivity at an A-MWCNT loading of 1.0 and 2.0 wt%. Continuously increasing thermal transport properties were observed with the 49.1 vol.% Al2O3 loading which derived from a lower interface density nanowire and polymer matrix with enhanced interconnectivity.