An innovative wire-arc additive manufacturing (WAAM) process is used to fabricate Cu-9 at. pct Al on pure copper plates in situ, through separate feeding of pure Cu and Al wires into a molten pool, which is generated by the gas tungsten arc welding (GTAW) process. After overcoming several processing problems, such as opening the deposition molten pool on the extremely high-thermal conductive copper plate and conducting the Al wire into the molten pool with low feed speed, the copper-rich Cu-Al alloy was successfully produced with constant predesigned Al content above the dilution-affected area. Also, in order to homogenize the as-fabricated material and improve the mechanical properties, two further homogenization heat treatments at 1073 K (800 °C) and 1173 K (900 °C) were applied. The material and mechanical properties of as-fabricated and heat-treated samples were compared and analyzed in detail. With increased annealing temperatures, the content of precipitate phases decreased and the samples showed gradual improvements in both strength and ductility with little variation in microstructures. The present research opened a gate for in-situ fabrication of Cu-Al alloy with target chemical composition and full density using the additive manufacturing process.