Pore and surface diffusion of carbon dioxide (CO2) and ethylene (C2H4) in the nanopores of ordered mesoporous silica fibers about 200 mu m in length was measured by the transient gravimetric method. The experimentally determined pore diffusivity data, coupled with the porosity, pore size, and fiber length, are used to obtain the actual length of the nanopores in silica fibers. These measurements reveal a structure of the ordered nanopores whirling helically around the fiber axis with a spiral diameter of about 15 mu m and a pitch value of 1.6 mu m. At room temperature the surface diffusion contributes about 10% to the total diffusional flux for these two gases in the nanopores of the ordered mesoporous silica fibers. The surface diffusion coefficients for the ordered mesoporous silica fibers are about 1 order of magnitude larger than the nonordered mesoporous alumina or silica with similar pore size.