Saturation exponent is an important parameter in Archie’s equations; however, there has been no well-accepted physical interpretation for the saturation exponent. We have theoretically derived Archie’s equations from the Maxwell–Wagner theory on the assumption of homogeneous fluid distribution in the pore space of clay-free porous rocks. Further theoretical derivations showed that the saturation exponent is in essence the cementation exponent for the water–air mixture and is quantitatively and explicitly related to the aspect ratio of the air bubbles in the pores. The results have provided a theoretical backup for the empirically obtained Archie’s equations and have offered a more physical and quantitative understanding of the saturation exponent.