Using Layered double hydroxides (LDH) nanoparticles and film-forming latexes, waterborne nanocomposite films were produced by simply a heterocoagulation and solvent casting process. Self-standing and transparent films with LDH contents from 2.5 to 15 vol% were prepared. The structure, microstructure and mechanical behavior were thoroughly investigated by powder X-ray diffraction (PXRD), infrared spectroscopy (IR), transmission electron microscopy (TEM), scanning electron microscopy (FIB–SEM) and dynamic mechanical analysis (DMA). Favorable electrostatic interactions between pristine LDH and the latex ensured a good dispersion of the bidimensional LDH platelets in the films. Above a certain content of LDH, the formation of a well-defined cellular LDH network following the starting latex morphology was observed. Such a percolating microstructure induces a large mechanical reinforcement significant of a mechanical percolation behavior.