The corrosion behavior of Al87Co7Ce6 alloy was investigated in the amorphous as-quenched, amorphous thermally relaxed, and two partially devitrified conditions using AC and DC electrochemical methods combined with high resolution microscopy in the active dissolution and passivity-local breakdown regimes. The best corrosion resistance was observed after relaxation. Intermediate behavior was observed in a partially devitrified treatment that formed small fcc Al particles and intermetallic phases. Further devitrification decreased the corrosion resistance. The amorphous “relaxed condition”, characterized by EXAFS, is an Al–Co–Ce solid solution with short bond length, high coordination number and reduced free volume compared to the as-quenched amorphous state.