Abstract This thesis is focused on the hydrolysis of aluminium, the polymerisation of the hydrolysis products, and how these can be monitored by mass spectrometric methods. The main aim of this research is to figure out how the aqueous speciation of aluminium changes as a function of pH (3.2–10), concentration (1–100 mM), reaction time (1s–14d), and counter anion (Cl-, SO42-, HCOO-). The method used was electrospray mass spectrometry. The results showed more variable speciation than those suggested earlier. The main species were Al2, Al3, and Al13, which were found in all of the conditions under scrutiny. The effect of pH was the most remarkable of all the parameters researched. The formation of large highly charged complexes was strongly dependent on it. Also the Al-concentration in the bulk solution had a clear effect on speciation: in dilute solutions there were more protonated ligands and less attached counter anions. This could mean that the species in more diluted bulk solutions had fewer different states of charge. Reaction time caused only minor changes to speciation in the initial pH: there was slightly more variation of a certain sized species in the aged solution. In elevated pH, the birth of important Al13 oligomers was time dependent. The effect of the counter anion was tremendous. In a chloride environment the speciation was rich and diversified. With sulphate the speciation was limited to solid- like compounds, and the variation of single-sized species was almost lacking. The formate as a counter anion caused most surprising results; the charge of aluminium in some studied complexes was lowered from the common 3+ to 1+. If this reaction also occurs in natural circumstances, the uses of aluminium formate would be wide. The results can be utilised in following the progress of dissolution, the mobilization and toxicity of aluminium in natural waters, as well as in water purification, and in reaching minimal chemical contamination levels in sludge as well as in aqueous waste.