Solid-state 27Al MAS NMR spectra enable to distinguish Al bound to organic compounds from that incorporated in secondary mineral phases detected by FTIR. MQMAS experiments additionally show that both chemical shifts and quadrupolar constants are distributed for Al nuclei linked with organic compounds. Similar amounts of chelated Al are obtained from NMR spectra and chemical extractions. The study enables to highlight three major steps in the fate of aluminum. (i) Aluminum is first released by mineral weathering, feeds complexing sites of organic matter and accumulates in subsurface Bhs horizons of weakly expressed podzols (acidocomplexolysis). (ii) Complexes of aluminum with organic matter (Al–OM) then migrate downwards in sandy horizons of better-expressed podzols and accumulate at depth in less permeable 2BCs horizons. (iii) The minor amounts of aluminum present in the 2BCs horizon of the downslope podzol show that aluminum is eventually exported towards the river network, either complexed with organic matter or as Al3+ ions after desorption from organic compounds, due to decreasing pH or biodegradation of organic ligands. The direct spectroscopic determination of Al-speciation during the formation of podzolic soils opens new perspectives to trace metal loads in the rivers of the upper Amazon Basin.