Recently, Chen et al. have suggested that the Eu³⁺ ion luminescence from f-f transitions could be used as an alternative to x-ray diffraction in the determination of crystal structure. From the results of the room-temperature luminescence data for three different host crystals only, the authors claim that this method is easier and can be more quickly performed than the usual powder diffraction technique. However, the spectra have not been convincingly assigned and are utilized as "finger-prints" of structure types. Our literature survey has indicated that all the data have been previously reported in the literature. In this note we critically comment on the paper and correct some errors and misconceptions therein. Our main conclusion is that the luminescence crystal structure determination cannot be regarded as an alternative "shortcut" method to the crystallographic structure determination for several reasons.

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