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The water absorption behavior, mechanical and thermal properties of vinyl ester matrix nanocomposites based on layered silicate were investigated. To characterize interlaminar structure of the nanocomposites, XRD, SEM, EDS, and TEM were performed. The mechanical and thermal properties of neat sample were improved by the incorporation of layered silicate. The improvement of the water repellence behavior was observed for the nanocomposites. The hardness and elastic moduli after water absorption was reduced due to the effect of water molecules entering into the polymer chains. However, the higher amount of clay reinforcement led to less reduction in hardness since the barrier properties.