A new method of in situ synthesis and thermal expansion was developed for preparing high-density polyethylene/exfoliated graphite composite. In the processes, an expandable composite was manufactured by high-density polyethylene and expandable graphite via the in situ synthesis. And then the final composite was prepared by the product obtained previously via the thermal expansion. The experimental results showed that the resistance values of the composite reached 2.58×107, 2.50×107, 2.46×107, 2.41×107, 2.34×107, 2.31×107, 2.27×107, 2.22×107 and 2.18×107 Ω and the expansion volumes of the composite were of 14.0, 15.0, 16.0, 16.3, 17.0, 18.1, 19.0, 20.0 and 22.0 ml g−1 when the mass ratios were 10:1.0, 10:1.5, 10:2.0, 10:2.5, 10:3.0, 10:3.5, 10:4, 10:4.5 and 10:5.0 and the expansion temperature was at 160°C. This shows that all of the resistance values are at 107 Ω, so the composite has the antistatic performance.