The Rietveld X-ray diffraction analysis was applied to analyze the weight fraction of precipitation phases and microstructure characterizations of rapidly solidified Al-8Zn-4Mg-xCu, x = 1, 4, 8, and 10 alloys (in wt.%), prepared by melt spun technique. A good agreement between observed and calculated diffraction pattern was obtained and the conventional Rietveld factors (Rp, Rwp, and GOF) converged to satisfactory values. Solid solubilities of Zn, Mg, and Cu in α-Al were extended to high values. Besides, metastable Al0.71Zn0.29, intermetallic Al2CuMg, Al2Cu, and CuMgZn phases have been observed for x = 4, 8, and 10 Cu alloys. The crystal structure and microstructure characterizations exhibit strong Cu content dependence.