Organophilic clay particles were added to a standard intumescent formulation and, since the role of clay expansion or intercalation is still a matter of much controversy, several clays with varying degrees of interlayer distances were evaluated. The composites were obtained by blending the nanostructured clay and the intumescent system with a polyethylenic copolymer. The flame-retardant properties of the materials were evaluated by the limiting oxygen index (LOI), the UL-94 rating and thermogravimetric analysis (TGA). The results showed that the addition of highly expanded clays to the ammonium polyphosphate and pentaerythritol formulation does not significantly increase the flame retardancy of the mixture, when measured by the LOI and UL-94. However, when clays with smaller basal distances were added to the intumescent formulation, a synergistic effect was observed. In contrast, the simple addition of clays to the copolymer, without the intumescent formulation, did not increase the fire retardance of the materials.