A supported membrane and a xerogel derived from 1,2-bis(triethoxysilyl)ethane (BTESE) under the same conditions were characterized by a gas uptake technique and membrane permeation method, respectively, to investigate the transport mechanism inside the pores. The results indicated that the transport in both materials was governed by repulsive necks, with more adsorptive gases experiencing stronger restrictions. Furthermore, on the basis of a comparison between the two samples, the similarity of activation energies for spherical gases provided positive evidence for the commonly used assumption of pore network equivalence between xerogels and membranes derived under the same conditions. Finally, the neck dimensions in both materials were evaluated by the GT-based model, and a mean value of approximately 2.90 angstrom (center-to-center distance) was obtained.