ABSTRACT The effects of La microalloying on the microstructure and corrosion behavior of as‐cast Cu–2.3Ni–0.6Si alloy in 3.5 wt.% NaCl solution were investigated through OM, XRD, SEM, EDS, and an electrochemical workstation. Results indicate that as the La content increased from 0.05 to 0.20 wt.%, the as‐cast microstructure of the alloy initially coarsens and subsequently refines. La not only aggregates near the Ni₂Si phase but also induces a preferred crystallographic orientation in in the Cu–2.3Ni–0.6Si alloy. Electrochemical corrosion results demonstrate that Cu–2.3Ni–0.6Si–0.05La exhibits optimal corrosion resistance in 3.5 wt.% NaCl solution, achieving the highest charge transfer resistance (1974 Ω·cm²), the maximum polarization resistance (292.31 kΩ·cm²), and the lowest corrosion current density (1.49 µA·cm⁻²). The improved corrosion resistance is attributed to the combined effects of La's purification role and its promotion of preferential growth of low‐index crystallographic planes with high planar density during solidification.