The flame-retardant properties of polydimethylsiloxane (PDMS)/oxidised multi-walled carbon nanotubes (MWCNT–COOH) nanocomposite films were dispersed using a nonionic acrylate copolymer surfactant. The nanocomposite films were prepared by spin coating and characterised using SEM, quasi-elastic cold-neutron scattering, TGA–FTIR, cone calorimetry, and LOI. The PDMS/surfactant/MWCNT–COOH (PSM) nanocomposite displayed superior flame-retardant performance compared to materials containing only surfactant or MWCNT–COOH. The peak heat release rate, the peak smoke production rate, total smoke release rate, carbon monoxide, and carbon dioxide production from PSM were 42, 47, 18, 28, and 47% less than the PDMS control. The LOI results for PSM exhibited a value of 32% with respect to 25% for the PDMS. PSM suppresses the smoke emission and inhibits penetration of the air reacting with the gas volatiles of the material. These new nanocomposites provide a valuable improvement in flame-retardant capabilities by physical barrier effect compared to other PDMS polymer materials.