The influence of organics on the crystallization of Al precipitates has been well documented. However, the effects of organics and ageing on the transformation and structural configuration of Al precipitates in relation to their surface and charge properties are not fully understood. This study investigated the structural, microporous and surface properties of Al precipitates formed under the influence of tannate and ageing. The Al precipitates were synthesized at an initial Al concentration of 7 × 10−3 M, an OH/Al molar ratio (MR) of 3.0, and initial tannate/Al MRs of 0, 0.001, 0.01 and 0.1, and aged for 1, 10 and 40 days. As indicated by a decrease in gibbsite and bayerite and an increase in the oxalate-extractable Al contents, the non-crystalline precipitates increased with the increase of the initial tannate/Al MR. This observation is in accord with the X-ray diffraction and Fourier transform infrared (FTIR) data. The impact of tannic acid on the nature of the Al precipitates is also reflected in the increase of the contents of the pyrophosphate-extractable Al, which is indicative of organically bound Al. This observation is in agreement with the increase in the intensity of characteristic FTIR absorption bands of tannate and the organic C and adsorbed water contents. The decrease in the crystallinity of Al precipitates with increase in the tannate/Al MR resulted in the development of microporosity, increase in BET specific surface area and decrease of the average pore diameter and point of zero salt effect (PZSE). The FTIR absorption bands characteristic of tannate of the Al precipitates became weaker with ageing, in accord with the ageing-induced decrease in the contents of organic C and pyrophosphate-extractable Al. Ageing drastically decreased the BET specific surface area of the Al precipitates formed in the absence of tannate but this effect was less conspicuous for the products formed at the tannate/Al molar ratio of 0.1. The ageing-induced change in the PZSE of the Al precipitates formed both in the absence and presence of tannate was not significant. The results accomplished in this study are of fundamental significance to our understanding of the combined effects of organics and ageing on structural configuration of hydrolytic precipitates of Al in relation to their microporosity, surface and charge properties in the environment.