In this study, the preparation of Al-pillared montmorillonite(Al-Mt) was conducted using aluminum salt reacting with montmorillonite(Na-Mt). Meanwhile, the thermally treated Al-pillared montmorillonite samples(Al-Mt-X) at different temperatures(200~600℃) were characterized using X-ray diffraction(XRD) and infrared spectra(FTIR) methods. The reductive transformation of 2-nitrophenol(2-NP) by Fe(Ⅱ)/the thermally treated Al-pillared montmorillonite complex system was investigated, with a consideration of the effects of calcination temperature, surface acid sites and solution pH on the transformation efficiency of 2-NP. The results showed that, with increasing calcinations temperature, the surface acid sites of Al-Mt-X were gradually reduced, and thus the reduction transformation efficiency of 2-NP was enhanced. As the calcination temperature was higher than 500℃, Fe(Ⅱ) and the thermally treated Al-pillared montmorillonite(Al-Mt-X) formed an Fe(Ⅱ)/Al-Mt-X complex system that could effectively improve the reaction capability of Fe(Ⅱ) species for 2-NP reductive transformation. In addition, the reduction transformation of 2-NP by the Al-Mt-X complex system could be described well by the pseudo first-order kinetic equation. The reaction apparent constant(k) of 2-NP reduction was increased with the increasing calcination temperature and solution pH. Therefore, the thermally treated Al-pillared montmorillonite as functional materials can effectively improve the reductive capability of the adsorbed species of Fe(Ⅱ) to degrade pollutants in an anaerobic environment. It should be indicated that the calcination temperatures and solution pH were two important impact factors.