The precipitation sequence of η(MgZn2) phase along low-angle grain boundaries in Al-Zn-Mg-Cu alloy was investigated by examining samples aged at 135 ℃ for various times from 5 min to 6 h. High resolution transmission electron microscopy (HRTEM) observations and energy dispersive X-ray spectroscopy (EDX) analysis indicate that the precipitation sequence of η phase along low-angle grain boundaries should be supersaturated solid solution (SSS)→vacancy-rich clusters (VRC)→GP Ⅱ zones→η'→η. Based on the theory of non-equilibrium grain boundary segregation (NGS) and non-equilibrium grain boundary co-segregation (NGCS), the excessive solute elements gradually segregate to the grain boundaries by the diffusion of the solute-vacancy complex during aging treatment. The grain boundary segregation plays an important role in the nucleation and growth of VRC, GP Ⅱ zones, η' phase as well as η phase.