In the present paper, the effective thermal conductivities of Li4SiO4-packed beds with both ordered and random packing structures were investigated using thermal resistance network methods based on both an Ohm’s law model and a Kirchhoff’s law model. The calculation results were also validated and compared with the numerical and experimental results. Firstly, it is proved that the thermal resistance network method based on the Kirchhoff’s law model proposed in the present study is reliable and accurate for prediction of effective thermal conductivities in a Li4SiO4-packed bed, while the results calculated with the Ohm’s law model underestimate both ordered and random packings. Therefore, when establishing a thermal resistance network, the thermal resistances should be connected along the main heat transfer direction and other heat transfer directions as well in the packing unit. Otherwise, both the total heat flux and effective thermal conductivity in the packing unit will be underestimated. Secondly, it is found that the effect of the packing factor is remarkable. The effective thermal conductivity of a packed bed would increase as the packing factor increases. Compared with random packing at similar packing factor, the effective thermal conductivity of packed bed would be further improved with an ordered packing method.