Traditional dual porosity models do not take into account the effect of matrix block size distribution on the mass transfer between matrix and fracture. In this study, we introduce the matrix block size distributions into an advective–diffusive solute transport model of a divergent radial system to evaluate the mass transfer shape factor, which is considered as a first-order exchange coefficient between the fracture and matrix. The results obtained lead to a better understanding of the advective–diffusive mass transport in fractured porous media by identifying two early and late time periods of mass transfer. Results show that fractured rock matrix block size distribution has a great impact on mass transfer during early time period. In addition, two dimensionless shape factors are obtained for the late time, which depend on the injection flow rate and the distance of the rock matrix from the injection point.