Interconnected microcellular polymeric monoliths have been prepared from oil-in-water concentrated emulsions of aqueous 1-vinyl-1,2,4-triazole using the high internal phase emulsion methodology. The polyHIPE materials thus obtained present a typical polyHIPE morphology having unexpectedly high mechanical strengths considering their low cross-linking level (3 mol % of N,N'-methylenebis(acrylamide)).(13)C, (15)N, and (1)H solid-state NMR analyses confirm the expected polymer structure and evidenced the presence of polymer chain association by strong hydrogen bonding with water.