This study suggests promising candidates as highly thermally conductive adhesives for advanced semiconductor packaging processes such as flip chip ball grid array (fcBGA), flip chip chip scale package (fcCSP), and package on package (PoP). To achieve an extremely high thermal conductivity (TC) of thermally conductive adhesives of around 10 Wm−1K−1, several technical methods have been tried. However, there are few ways to achieve such a high TC value except by using spherical aluminum nitride (AlN) and 99.99% purified aluminum oxide (Al2O3) fillers. Herein, by adapting highly sophisticated blending and dispersion techniques with spherical AlN fillers, the highest TC of 9.83 Wm−1K−1 was achieved. However, there were big differences between theoretically calculated TCs that were based on the conventional Bruggeman asymmetric model and experimentally measured TCs due to the presence of voids or pores in the composites. To narrow the gaps between these two TC values, this study also suggests a new experimental model that contains the porosity effect on the effective TC of composites in high filler loading ranges over 80 vol%, which modifies the conventional Bruggeman asymmetric model.