An organic-inorganic hybrid monolithic column based on 1-vinyl-3-dodecylimidazolium bromide (VC12Im(+)Br(-)) has been prepared in a single step by combining radical copolymerization with a non-hydrolytic sol-gel (NHSG) process. The NHSG process was significantly shortened to 6 h by using formic acid as catalyst. For comparison, we also prepared polymeric ionic liquid (PIL) monolithic columns by hydrolytic sol-gel and organic polymeric process, respectively. The resulting monolithic columns were characterized by Fourier transform infrared spectra, scanning electron microscopy, and Brunauer-Emmett-Teller. Under the capillary electrochromatography mode, these columns were applied to separate alkylbenzenes, anilines, and proteins, respectively. The results indicated that the NHSG-based hybrid PIL monolithic column exhibited the highest column efficiency among the three types of columns; organic solvent, commonly required by the traditional columns to achieve satisfactory separation efficiency for proteins, was absent in the NHSG-based hybrid PIL monolithic column because of the biocompatibility of the VC12Im(+)Br(-), which was beneficial to analysis of protein containing samples. In order to demonstrate its application potential, the developed NHSG-based hybrid PIL monolithic column was also employed to separate egg white sample.