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Tremendous effort has been devoted to tailoring structure-correlated properties, especially for the luminescence of lanthanide nanocrystals (NCs). High pressure has been demonstrated as a decent way to tune the performance of lanthanide NCs; however, little attention has been paid to the local structure evolution accompanied by extreme compression and its effect on luminescence. Here, we tailor the local structure around lanthanide ions with pressure in β-NaGdF4 NCs, in which Eu3+ ions were doped as optical probes for local structure f