Vinyl ester/clay nanocomposites with 1, 3, and 5% nanoclay contents were prepared. X‐ray diffractography patterns and Scanning Electron micrographs showed that nanocomposites with the exfoliated structure were formed. Thermogravimetric analysis, water absorption test, and Tafel polarization method, respectively, revealed the improvements in thermal resistance, water barrier properties, and corrosion resistance properties of the samples with an increase in the amount of the incorporated nanoclay. Tensile tests showed that nanoclay also enhanced the mechanical properties of the polymer, so that the tensile strength of the samples with 5% nanoclay was more than 3 times higher than tensile strength of pure vinyl ester samples. Overall, the best properties were observed for the samples containing 5% nanoclay. Pure vinyl ester and nanocomposite with 5% nanoclay content were exposed to the electron beam radiation and their mechanical properties improved up to 500 kGy irradiation dose. Finally, pure vinyl ester and vinyl ester/nanoclay (5%) matrixes were reinforced with carbon fiber and the effect of electron beam irradiation on their mechanical properties was examined. The tensile strength and the modulus of the samples initially increased after exposure to the radiation doses up to 500 kGy and then a decrease was observed as the irradiation dose rose to 1000 kGy. Moreover, nanoclay moderated the effect of the irradiation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42393.