In this work, starch-clay-TiO2-based nanocomposites were deposited on cotton fabric through layer-by-layer (LBL) process and their effect on the flame retardancy, inhibition of pyrolysis and combustion processes were discussed in details. Polyelectrolyte solutions/suspensions of cationized starch and VMT (vermiculite)/TiO2 nanoparticles were used to deposit these nanocomposites in the form of multi-layered coatings (5, 7, 10 and 15 bilayers). Uniform fabric coverage and presence of electrolytes was imaged by scanning electron microcopy (LVSEM), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and EDX characterizations. The greatest pyrolysis reduction was found for the StVT-7 sample (7 bilayers); -30% and 21%, based on microscale combustion calorimetry (MCC) and thermogravimetric analysis (TGA). When using MCC, the improved values of the PHRR - 193 W/g, THR - 10.7 kJ/g), HRC - 390 J/g center dot K and LOI - 22.2% were found for the StVT-7 sample which was strongly supported by the UL-94 test.