© 2016 Wiley Periodicals, Inc.The application of polymeric high-internal-phase emulsion (polyHIPE) capillary coatings for open-tubular analytical separation columns was demonstrated in this study for the first time. Multiple polystyrene-co-divinylbenzene polyHIPE layers with an average total depth of 1.73 µm were coated onto internal capillary surfaces to create open-tubular columns (20 cm coating and 32.5 cm effective length). With these columns for open-tubular capillary electrochromatography, ethylbenzene and pentylbenzene were separated. Although the overall separation capacity of the produced columns was low, the polyHIPE coatings improved the analyte peak shape, decreased the total run time, and improved the peak symmetries relative to comparable unmodified open-tubular columns. In addition, the use of these novel polyHIPE columns led to the use of 30% less organic modifier. These columns have the potential to improve the shelf life of open-tubular columns typically used in capillary electrochromatography. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44237.