Organic-silica hybrid monolithic columns have drawn more and more attention due to the ease of preparation and good mechanical stability in recent years. Many synthetic approaches have been developed and a variety of hybrid monolithic capillary columns have been prepared. The sol-gel process is well recognized in the fabrication of hybrid monolithic columns, which can be mainly classified as one-step, acid/base two-step procedures. The new approaches such as the " one-pot'' and nano-scaled inorganic-organic hybrid reagent of polyhedral oligomeric silsesquioxane used as a cross-linker have also emerged for the preparation of hybrid monolithic columns. The applications of the organic-silica hybrid monolithic capillary columns for capillary electrochromatography, micro high-performance liquid chromatography, solid-phase microextraction and enzymatic reactor etc. are included in this review.