A natural and synthetic layered silicate (LS) was modified with trihexyltetradecyl‐phosphonium tetrafluoroborate (an ionic liquid) via a cationic exchange reacation. The exchange reaction and loading of modifier was investigated using a combination of WAXD, inductively coupled plasma‐optical emmission spectroscopy (ICP‐OES) and thermogravimetric analysis (TGA). The thermal stability of the modified LS was enhanced by up to 150 °C, when compared with conventional quaternary ammonium cations, making melt mixing of such modified nanoclays possible with poly(ethylene‐terephthalate) (PET).