Two organophilic bentonites, based on nitrogen-containing compounds, have been synthesised via ion exchange starting from pristine bentonite with octadecyltrimethylammonium bromide (OTAB) and with synthetic melamine-derived N2,N4-dihexadecyl-1,3,5-triazine-2,4,6-triamine (DEDMEL). The chemical and morphological characterization of the organoclays was based on XRD, TEM, Laser Granulometry, X-Ray Fluorescence and CEC capacity. Copoly(styrene-butadiene-styrene)-nanocomposites (SBS-nanocomposites) were obtained by intercalation of the SBS-copolymer into these new organoclays by melt intercalation method. XRD and TEM analysis of the organoclays and of the micro/nano-composites obtained are presented. The effect of the organoclays on the SBS-nanocomposite's flammability properties was investigated using cone calorimeter. An encouraging decrease of 20% in the peak heat released rate (PHRR) has been obtained confirming the important role of melamine's based skeleton and its derived organoclays to act as effective fire retardants and for the improvement of this important functional property in SBS copolymers.