This simultaneous separation of basic, acidic and neutral analytes by pressure-assisted CEC (pCEC) using a hybrid (tetramethoxysilane and methyltrimethoxysilane) silica-based monolith, chemically modified with octadecyldimethylchlorosilane followed by endcapping with hexamethyldisilazane is described. The endcapping resulted in near Gaussian peaks for highly basic analytes such as nortriptyline without a significant loss in the EOF. The migration behaviour of analytes on this phase could be rationalised based on hydrophobicity, electrophoretic mobility and ion-exchange interactions. The high porosity of the monolith allowed manipulation of the linear velocity of mobile phases by the addition of varying amounts of pressure at the inlet to reduce analysis times and overcome the reversed migration of anionic species towards the detection window in cathodic EOF mode. The concomitant programmed application of pressure (2-4 bar) and voltage (27 kV) facilitated the simultaneous separation of four cationic, four neutral and two anionic compounds in 6 min with efficiencies ranging from 41000 to 94 000, 57 000 to 77 000 and 180 000 to 210000 theoretical plates/metre, respectively. The % RSD values of migration times and efficiencies in pCEC mode were less than 3.6 and 7.9%, respectively (n = 5).