The exfoliated poly(methyl acrylate-co-methyl methacrylate)/montmorillonite (MMT) nanocomposite latex solutions fabricated by soap-free emulsion polymerization were able to cast into a film. The films were transparent and ductile unless more than 5 wt% of MMT was incorporated. With the MMT content higher than 5 wt%, the inflammable residuals of nanocomposites after combustion could preserve their original film profile acting like an inflammable scaffold. Moreover, as 20 wt% MMT was incorporated, the yield strength of the films was increased up to 20 times and Young’s modulus up to 2,000 times. However, the water vapor permeability coefficient of the films was only decreased down to its half value. This unexpected behavior of permeability was associated with the decrease of T g as the content of MMT was increased, owing to the large difference of the reactivity ratios between methyl acrylate and methyl methacrylate monomers and their differential absorption to the MMT during copolymerization.