This work presents a new analytical system to study the electrophoretic mobility of gold nanoparticles with different sizes, in which the platinum-coated alumina membranes are used as the separator due to the high pore densities, rigid support structure, chemical and thermal stability. It is shown that the electrophoretic mobility of gold nanoparticles is dependent on the nature of mobile phase and interfacial properties of alumina channels. The transport performance of nanoparticles are improved with the addition of sodium dodecyl sulfate (SIDS) into the mobile phase, because SDS not only decreases the physical adsorption of gold nanoparticles on the nano-channel wall of alumina membrane, but also reduces the thickness of the electric double layer (decreasing the apparent size of particles). When the alumina membranes were modified with 6-aminohexanoic acid, it was further confirmed that the physical adsorption played a key role for the electrophoretic mobility of gold nanoparticles. Under optimized conditions, the mobility of gold nanoparticles had a fairly linear dependence on particle size (R-2 > 0.99), reiterating that our membrane system was also capable of characterizing gold nanoparticles in nanometer-size regimes. (C) 2008 Elsevier B.V. All rights reserved.