One of the issues arising in materials science is the behavior of nonequilibrium point defects in the atomic lattice, which defines the rates of chemical reactions and relaxation processes as well as affects the physical properties of solids. It is previously theoretically predicted that melting and rapid solidification of metals and alloys provide a vacancy concentration in the quenched material, which can be comparable to that quantity at the point of melting. Here, the vacancy behavior is studied experimentally in thin films of the near equiatomic Fe–Al alloy subjected to nanosecond laser annealing with intensities up to film ablation. The effects of laser irradiation are studied by monitoring magneto‐optically the ordering kinetics in the alloy at the very ablation edge, within a narrow (micron‐scale) ring‐shaped region around the ablation zone. Quantitatively, the vacancy supersaturation in the quenched alloy has been estimated by fitting a simulated temporal evolution of the long‐range chemical order to the obtained experimental data. Laser quenching (LQ) of alloys and single‐element materials will be a tool for obtaining novel phase states within a small volume of the crystal.