The complex interplay of electrophoretic, electroosmotic, bulk convective, and diffusive mass/charge transport in a hybrid poly(dimethylsiloxane) (PDMS)/glass microchannel with embedded floating electrode is analyzed. The thin floating electrode attached locally to the wall of the straight microchannel results in a redistribution of local field strength after the application of an external electric field. Together with bulk convection based on cathodic electroosmotic flow, an extended field gradient is formed in the anodic microchannel segment. It imparts a spatially dependent electrophoretic force on charged analytes and, in combination with the bulk convection, results in an electric field gradient focusing at analyte-specific positions. Analyte concentration in the enriched zone approaches a maximum value which is independent of its concentration in the supplying reservoirs. A simple approach is shown to unify the temporal behavior of the concentration factors under general conditions.