The Al13 polycation is the predominant hydroxy-Al species in partially neutralized solutions. However, the existence of the Al13 species and the factors governing its formation in terrestrial environments still remain obscure. The objective of this study was to investigate the influence of pyrogallol, a common polyphenol in soils, on the formation of Al13 tridecamer. Hydroxy-Al solutions with an OH/Al molar ratio of 2.2 (pH 4.53) at pyrogallol/Al molar ratios of 0, 0.01, 0.05, 0.1 and 0.5 were prepared and mixed with 0.5 M sodium sulfate to form aluminum sulfate precipitation products. The solid-state 27Al nuclear magnetic resonance (NMR) spectra of the precipitates show that the pyrogallol perturbed the formation of Al13 tridecamer species as indicated by the decrease in the intensity of resonance peak, observed at 62.5 ppm, with increase in the pyrogallol/Al molar ratio. The crystallization of the precipitated Al sulfates was also hampered by pyrogallol, resulting in the formation of X-ray non-crystalline products at a pyrogallol/Al molar ratio of 0.50. The absorbance at 465 and 650 nm of the hydroxy-Al-pyrogallol solutions, the C coprecipitated, the electron spin resonance and 13C CPMAS-NMR spectra of the precipitates indicate the concomitant enhanced abiotic humification of pyrogallol by the X-ray amorphous Al species.