The study presents a new analytical method for speciation analysis in fractionation of aluminium fluoride complexes and free Al(3+) in soil samples. Aluminium speciation was studied in model solutions and soil extract samples by means of high performance ion chromatography (HPIC) with UV-VIS detection using post-column reaction with tiron for the separation and detection of aluminium fluoride complex and Al(3+) forms during one analysis. The paper presents particular stages of the chromatographic process optimization involving selecting the appropriate eluent strength, type of elution or concentration and quantity of derivatization reagent. HPIC was performed on a bifunctional analytical column Dionex IonPac CS5A. The use of gradient elution and the eluents A: 1M NH(4)Cl and B: water acidified to pH of eluent phase, enabled full separation of fluoride aluminium forms as AlF(2)(+), AlF(3)(0), AlF(4)(-) (first signal), AlF(2+) (second signal) and form Al(3+) in a single analytical procedure. The proposed new method HPIC-UVVIS was applied successfully in the quantitative and qualitative analysis of soil samples.