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The low crystallization rate and long molding time of poly(ethylene terephthalate) (PET) restricts its application in the field of engineering plastics. PET/graphene oxide (GO) composites were synthesized through in situ polymerization method with dimethyl terephthalate (DMT), ethylene glycol (EG) as reactants and GO as filler in order to overcome the above shortcomings. Influence of GO on the crystallization performance of PET was investigated. It was revealed GO raised the crystallization temperature and crystallization rate of PET, demonstrating the excellent nucleation capability of GO. The mechanism of PET nucleation induced by GO was investigated by Avrami equation and Hoffman-Lauritzen theory. It was obvious the crystallization behavior of PET was improved by reducing the free energy of nucleation and the fold surface free energy of PET caused by GO. Moreover, the non-isothermal kinetics of thermal decomposition of PET and PET/GO composites were studied by Friedman method. It was obvious that all of PET and PET/GO composites exhibited a fine thermal stability with no significant mass loss observed up to 370 °C (< 0.5%). The addition of GO improved the thermal stability of PET through raising the apparent activation energy, inhibiting the escape of volatile products and absorbing the degradation products in PET thermal decomposition procedure. [ABSTRACT FROM AUTHOR]