In this work, zinc borate was used as a flame retardant in ethylene vinyl acetate/magnesium hydroxide or aluminum hydroxide flame-retardant formulations. High content zinc borate leads to significant improvements of flame retardancy through limiting oxygen index, UL-94 and cone calorimeter experiments. The protective char formation revealed significant structural modifications due to the presence of zinc borate. It was demonstrated that during polymer heating, aluminum hydroxide and magnesium hydroxide decomposed to Al2O3 and MgO which resulted an increase in ignition time. Moreover, formation of Al2O3 or MgO in situ from aluminum hydroxide or magnesium hydroxide during polymer combustion is the first event. Concurrently, zinc borate degraded and formed a vitreous protective coating, which yielded the substrate with an efficient char which acted as a physical barrier and a glassy cage for better protection of polymer substrate. © The Author(s) 2013 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.