This paper describes the development of silica monolithic column modified with ionic liquids-gold nanoparticles (ILs-GNPs) for capillary electrochromatography (CEC). The novel ILs (1-methyl-2-mercapto-3-butylimidazolium bromide) were synthesized and used to modify GNPs functionalized silica monolithic column via the formation of a Au–S bond. The morphology of the GNPs and ILs-GNPs functionalized silica (ILs-GNPs-silica) monolithic column were characterized by transmission electron microscopy and scanning electron microscope, respectively. A cathodic electroosmotic flow was observed at pH above 6.4 on ILs-GNPs-silica monolithic column, which was reversed at acidic pH. The electrochromatographic performance of ILs-GNPs-silica monolithic column was evaluated by separation of different kinds of analytes such as hydrophobic, polar and basic compounds. The ILs-GNPs-silica monolithic column displayed enhanced hydrophobic retention characteristics in the separation of five hydrophobic n-alkylbenzenes when compared to the ILs bonded silica monolithic column. The column efficiencies for the n-alkylbenzenes were from 62 000 to 110 000 N m⁻¹. The ILs-GNPs-silica monolithic column exhibited reversed-phase electrochromatographic behavior toward neutral solutes. Separation of polar compounds was demonstrated on ILs-GNPs-silica monolithic column in reversed-phase CEC mode using high aqueous mobile phases. The relatively good peak shape and high separation efficiency on ILs-GNPs-silica monolithic column was obtained for basic solutes when compared to silica monolithic column modified GNPs.