Abstract Insoluble sulfur (IS) is prepared at low temperature with graphene oxide (GO) as stabilizer and ammonium persulfate as initiator. The FTIR and Raman patterns show that the non-conjugate double bond of GO can couple to the long chain free radicals of IS. The TGA and EDS results show that the mass fraction of IS is 79.75 wt% in particles by refluxing method, much higher than that in particles by hydrothermal method, when the mass ratio in reactants of GO to sulfur was 3: 1. Under constant content of sulfur, the tensile stress and elongation at break of NBR/GO-S(h) and NBR/GO-S(r) composites are higher than those of NBR/Reduced GO composites with the addition of 3 phr GO-S(h), GO-S(r) and Reduced GO particles into NBR. It can provide a new technology for the preparation of IS with lower temperature, little energy consumption and less environmental pollution. It is also a new method for the modification and application of GO in rubber.