Control of the EOF in electroseparation techniques can be applied to improve separation and sensitivity. Coating of the inner capillary wall is often used to modify and control the electroosmotic bulk flow properties. Here, the applicability of a hydrogel at one end of a fused silica capillary for electrophoretic analysis in three CE modes and under neutral conditions is demonstrated. Firstly, in counter-EOF CZE, the migration order of anionic compounds was reversed. Secondly, inversion of the elution order was also achieved for neutral analytes in micellar electrokinetic chromatography using a negatively charged pseudostationary phase. Finally, field enhanced sample injection of three model compounds in counter-EOF CZE provided a sensitivity improvement of more than factor 500 compared to typical pressure injection.