Phase fraction and solidification path of high Zn-containing Al-Zn-Mg-Cu series aluminum alloy were calculated by calculation of phase diagram (CALPHAD) method. Microstructure and phases of Al-9.2Zn-1.7Mg-2.3Cu alloy were studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The calculation results show that η(MgZn2) phase is influenced by Zn and Mg. Mass fractions of η(MgZn2) in Al-xZn-1.7Mg-2.3Cu are 10.0%, 9.8% and 9.2% for x=9.6, 9.4, 8.8 (mass fraction, %), respectively. The intervals of Mg composition were achieved for θ(Al2Cu)+η(MgZn2), S(Al2CuMg)+η(MgZn2) and θ(Al2Cu)+S(Al2CuMg)+η(MgZn2) phase regions. Al3Zr, α(Al), Al13Fe4, η(MgZn2), α-AlFeSi, Al7Cu2Fe, θ(Al2Cu), Al5Cu2MgsSi6 precipitate in sequence by no-equilibrium calculation. The SEM and XRD analyses reveal that α(Al), η(MgZn2), Mg(Al,Cu,Zn)2, θ(Al2Cu) and Al7Cu2Fe phases are discovered in Al-9.2Zn-1.7Mg-2.3Cu alloy. The thermodynamic calculation can be used to predict the major phases present in experiment.