The effect of microstructures of interfacial layers on transport behaviors of particulate composites has been found to be significant, thus microstructural characteristics of interfacial layers should be considered in the analysis for better prediction of transport properties of particulate composites. However, it is very difficult to determine the volume fraction of soft interfacial layers around polydisperse three-dimensional (3D) ellipsoidal aggregate particles and to practically estimate the influence of such a microstructural characteristic on transport properties of particulate composites by traditional experimental methods and simple models proposed so far. In this article, an approximate analytical model for the volume fraction of soft interfacial layers is proposed on the basis of a theory of the nearest-surface distribution functions and geometric characteristics of polydisperse ellipsoidal particle systems. A theoretical model that adopts a three-phase composite ellipsoid structure by a generalized self-consistent scheme is further presented to predict the effective transport properties of particulate composites containing such soft interfacial layers. To test the developed models, numerical results of the soft interfacial volume fraction from the previous work, experimental data in the literature, the Hashin-Shtrikman bounds model and the Maxwell-Garnett model for the effective electrical conductivity are compared respectively. Finally, by virtue of the present models, the effects of key factors on the effective electrical conductivity of particulate composites are investigated in a quantitative manner.