Precipitation strengthening of body-center cubic (A2) alloys via ordered B2 nanoprecipitates is expected to achieve a desirable combination of strength and ductility. In this work, the A2/B2 configuration is manipulated by adjusting Fe content in medium-entropy AlCrFexNi (x = 0, 0.5, 1.0, 1.5, 2.0, 2.5 and 3.0) alloys fabricated via arc-melting for improved mechanical properties and wear resistance. As Fe content increases, the fraction of A2 phase increases, and A2 nanoprecipitates in the B2 matrix change to a weave-like A2/B2 structure. Continuously increasing Fe content leads to a mixture of BMAP (B2 matrix with A2 precipitates) and AMBP (A2 matrix with B2 precipitates), and finally to a complete AMBP structure. The yield strength decreases and fracture strain increases with increasing Fe content except x = 0. The alloy of x = 0 displays slightly higher hardness because of its relatively brittle B2 matrix. Cracks tend to propagate along A2/B2 interfaces. AMBP structure exhibits greater toughness than the BMAP structure. The alloy of x = 0 displays the second-greatest wear volume loss due to its relatively brittle B2 matrix. When Fe is added, the wear volume loss decreases considerably but shows a trend of an upward parabola with respect to the Fe content. After achieving the highest volume loss at x = 1.5 with a mixture of AMBP and BMAP, the volume loss decreases again. A completely uniform AMBP structure at x = 3.0 shows the least volume loss.