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Extended x‐ray absorption fine structure (EXAFS) measurement is the technique to measure nondestructively the nearest‐neighbor distance, to the accuracy within 0.01 Å or better, coordination number, and atomic species. Especially, fluorescence‐detected EXAFS is best suited to characterize the atomic scale microstructure of epitaxially grown thin layers on a thick substrate. We have investigated the microstructure for each atomic pair of Ga‐P, Ga‐As, and In‐As in (Ga,In)(As,P) alloys lattice‐matched with InP, over a wide range of composition from dilute limit, through quaternary, to ternary. Constant atomic distances over the wide range were revealed when the average lattice parameter was kept constant.