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Melamine‐modified montmorillonite (MA‐MMT) was prepared via cation exchange. The intercalation behavior was investigated by Fourier transform infrared spectrometer (FT‐IR), X‐ray photoelectron spectroscopy (XPS), and X‐ray diffraction (XRD). The results showed that the d‐spacing value increased from 1.25 nm for Na‐montmorillonite (Na+MMT) to 1.53 nm for MA‐MMT. Different kinds of montmorillonite combined with melamine pyrophosphate (MPP) were used to prepare flame‐retardant polyamide 6 (FR‐PA6). Flame retardance of FR‐PA6 samples was investigated by limiting oxygen index (LOI), UL‐94 vertical burning method, and cone calorimeter test. Morphology and component of char residues for FR‐PA6 were investigated by scanning electron microscope (SEM) and XPS. It was found that MA‐MMT/MPP system contributed both excellent flame retardance and anti‐dripping ability for PA6. MA‐MMT particles can fill flaws of char residues and strengthen the char layer, leading to form more intumescent char layer. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers