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Aluminium (Al) K‐ and L‐edge X‐ray absorption near‐edge structure (XANES) has been used to examine Al speciation in minerals but it remains unclear whether it is suitable for in situ analyses of Al speciation within plants. The XANES analyses for nine standard compounds and root tissues from soybean (Glycine max), buckwheat (Fagopyrum tataricum), and Arabidopsis (Arabidopsis thaliana) were conducted in situ. It was found that K‐edge XANES is suitable for differentiating between tetrahedral coordination (peak of 1566 eV) and octahedral coordination (peak of 1568 to 1571 eV) Al, but not suitable for separating Al binding to some of the common physiologically relevant compounds in plant tissues. The Al L‐edge XANES, which is more sensitive to changes in the chemical environment, was then examined. However, the poorer detection limit for analyses prevented differentiation of the Al forms in the plant tissues because of their comparatively low Al concentration. Where forms of Al differ markedly, K‐edge analyses are likely to be of value for the examination of Al speciation in plant tissues. However, the apparent inability of Al K‐edge XANES to differentiate between some of the physiologically relevant forms of Al may potentially limit its application within plant tissues, as does the poorer sensitivity at the L‐edge. [ABSTRACT FROM AUTHOR]