Computational Fluid Dynamics (CFD) was used to compare the micro scale heat transfer inside a packed bed and a microfibrous entrapped catalyst (MFEC) structure. Simulations conducted in stagnant gas determined the thermal resistance of the gas in the micro gaps between the particle-to-particle contact points in the resistance network model of a packed bed. Tube to particle diameter ratios for the simulations were 9 based on particle diameter and 27 for MFEC based on surface area average diameter. The maximum temperature difference used in the simulations was 80°C. It was shown that thermal resistance at the contact points accounted for 90% of the thermal resistance of the solid path. In the MFEC, the thermal resistance of the continuous metal fibers was relatively smaller than that of contact points. As a result, 97.2% of the total heat flux was transported by continuous fiber cylinders, which was the fundamental function of fibers on improving the heat transfer of MFEC structures. Enhanced heat transfer characteristics of MFEC were further demonstrated by simulations performed in flowing gas, where both heat conduction and heat convection were significant.