The exceptional sorption capabilities of carbon nanotubes were used to preconcentrate trace sulphonamides from milk samples. To this end, single walled carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs) dispersed in the ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate were retained on a C18 stationary phase to obtain a hybrid material in a simple manner. In this approach ionic liquids are an excellent alternative to improve the dispersion of CNTs, without chemical modification or the use of solid substances or organic solvents. MWNTs provided better results than SWNTs. Carbon nanotubes retained in the C18 sorbent matrix were found to confer aromatic character, increasing its preconcentration capacity as a result. The conventional C18 stationary phase played a two-fold role: as a support to retain carbon nanotubes in the cartridge and as a medium to prevent their aggregation. The modified MWNT/C18 and SWNT/C18 materials were used to preconcentrate residual sulphonamides (SAs) in milk samples for their determination at concentrations as low as 0.03–0.069 mg L⁻¹ by capillary electrophoresis. Analyte recoveries from spiked samples ranged from 103.2 to 98.8% and precision, as RSD, from 8.2 to 5.4%.