The advantages of cyanate esters (CEs) versus competitor systems such as epoxies and polyimides, as well as the great reinforcing potential of organoclays properly dispersed into a polymeric matrix, have been examined in a series of poly-cyanurate (PCN)/montmorillonite (MMT) nanocomposites prepared under appropriate polymerization conditions. The curing schedule applied resulted in gradual propagation of polymerization. Through this procedure, the intragallery curing rate becomes comparable to the extragallery one, allowing intercalation before gelation. Systems with clay loadings from 1 to 3% per weight were synthesized, and their morphology and mechanical properties were studied by means of scanning electron microscopy (SEM), atomic force microscopy (AFM), wide angle X-ray scattering (WAXS), dynamic mechanical analysis (DMA), and tensile tests. Microscopy investigations revealed better dispersion for the 3 wt % system compared to smaller concentrations, in which aggregation and, in some cases, agglomeration were the conspicuous features. Roughness and area analyses revealed more homogeneous dispersion for this nanocomposite. Topology and 3D-phase images further suggested considerable reduction of the average particle diameters. WAXS analysis showed that the interlayer spacing of nanocomposites was increased compared to pristine MMT, indicating the formation of intercalated structures. On the other hand, tensile strength and elongation at break values displayed abrupt diminution with MMT addition, while Young's modulus exhibited a slight but systematic increment with MMT content. The decreasing glass transition tendency observed for small clay loadings was reversed in the case of 3 wt %, while secondary transitions were practically unaffected by the presence of MMT. (c) 2008 Wiley Periodicals, Inc.