In reversed-phase liquid chromatography (RPLC), basic drugs are positively charged at the usual working pH range and interact with free anionic silanols present in conventional silica-based stationary phases. This translates into stronger retention and tailed and broadened peaks. This problem can be resolved by the addition of reagents to the mobile phase that are adsorbed on the stationary phase, avoiding the access of solutes to silanols. Among these additives, surfactants under micellar conditions have provided good silanol suppressing potency through the technique known as micellar liquid chromatography (MLC). The most common example of this is anionic sodium dodecyl sulphate (SDS). When SDS is at moderate concentration in the presence of high organic solvent content, micelles are not formed and the chromatographic mode is known as high submicellar liquid chromatography (HSLC). In contrast, the addition of an oil to an aqueous solution of SDS containing micelles gives rise to microemulsions in a chromatographic mode known as microemulsion liquid chromatography (MELC). A comprehensive comparison of the chromatographic behaviour of a set of basic β-adrenoceptor antagonists analysed by MLC, HSLC and MELC is carried out in this work, in terms of retention, peak shape and organic solvent consumption. The study shows that high submicellar eluents reduce retention and enhance efficiency with respect to conventional RPLC and MLC. Meanwhile, MELC allows reduced analysis times with less organic solvent with respect to HSLC. The narrower and more symmetrical peaks in MLC, HSLC and MELC, with respect to conventional RPLC, reveal the presence of silanol masking.