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In this study, montmorillonite (MMT) was used as an inorganic synergist to prepare the water-based intumescent flame retardant (IFR) ornamental coating for plywood. Results indicate that the 7 wt.% MMT modified IFR coating (No. 3) possess the best fire resistance (longer than 20 min) of the tested samples according to the fire performance, which significantly declines the specific extinction area by 44.12 m2·kg−1 compared to the coating without MMT by cone calorimeter. In addition, characterizations such as XPS, XRD, TG, SEM and FTIR were characterized to investigate the surface and bulk properties as well as the morphology of MMT synergized water-based IFR coating. It is revealed that the residual nitrogenous polyaromatic structure and 25.5% residual mass in the No. 3 coating are a result of the effect of MMT on the antioxidation properties of the char layer. [ABSTRACT FROM AUTHOR]