Separation possibilities of three-dimensional capillary electrophoresis

► The separation potentialities of 3D CE were examined. ► Phthalate and urine have been selected as a model analyte and matrix, respectively. ► 3D CE (ITP-ITP-CZE) has been compared to 2D CE (ITP-CZE). ► Increased dimensionality of 3D CE provided significant improvement in the separation selectivity/sample clean-up. ► 3D CE-UV represents an advanced separation tool for trace analyte in the unpretreated complex matrix.