In the present study, the influence of the addition of copper (Cu) on the wear behavior of a Al-12.6Si eutectic alloy developed using the spray forming (SF) method was discussed, and the results were compared with those of as-cast (AC) alloys. The microstructural features of the alloys were examined using both optical and the scanning electron microscopy, and the chemical composition and phase identification were achieved by X-ray diffraction (XRD) analysis. The results revealed that the microstructure of binary the SF alloy consisted of fine primary and eutectic Si phases, evenly distributed in the equiaxed α-Al matrix, whereas the Cu-based SF ternary alloy consisted of uniformly distributed fine eutectic Si particulates and spherical-shaped θ-Al2Cu precipitates, uniformly distributed in α-Al matrix. In contrast, the AC ternary (Al-12.6Si-2Cu) alloy consisted of unevenly dispersed eutectic Si needles and the coarse intermetallic compound θ-Al2Cu in the α-Al matrix. The addition of Cu enhanced the micro hardness of the SF ternary alloy by 8, 34, and 41% compared to that of the SF binary, AC ternary, and binary alloys, respectively. The wear test was conducted using a pin-on-disc wear testing machine at different loads (10–40 N) and sliding velocities (1–3 ms−1). The wear tests revealed that SF alloys exhibited an improved wear behavior in the entire applied load and sliding velocity range in comparison to that of the AC alloys. At a load of 40 N and a sliding velocity of 1 ms−1, the wear rate of the SF2 alloy is 62, 47, and 23% lower than that of the AC1, AC2, and SF1 alloys, respectively. Similarly, at a sliding velocity of 3 ms−1, the wear rate of the SF2 alloy is 52%, 42%, and 21% lower than that of the AC1, AC2, and SF1 alloys, respectively. The low wear rate in the SF2 alloy was due to the microstructural modification during spray forming, the precipitation of fine Al2Cu intermetallic compounds, and increased solid solubility. The SF alloys show an increased transition from oxidative to abrasive wear, while the AC alloys demonstrate wear mechanisms that change from oxidative to abrasive, including delamination, with an increase in sliding velocity and load.