Speciation analysis of aluminium in the presented system of HPLC–FAAS hyphenated technique lasts 4 min. Using the bifunctional column in model analysis and using the calculation methods for modelling using the Mineql program enabled the authors to presume that particular forms will be subjected to elution in the following order: (1) AlF2+ and AlF4−, (2) AlF2+ and AlF30 and (3) Al3+. Based on the obtained results for model solutions, the presented method enables the determination of aluminium fluoride complexes and Al3+ speciation form. The study compares the tendency of occurrence variability of aluminium fluoride complexes and Al3+ form, determined based on the results obtained using the HPLC–FAAS hyphenated technique with the trend defined based on the Mineql program calculation method. The method was successfully applied to soil samples.