Fe(III) (hydr)oxides commonly contained many metal impurities such as Al. The incorporation of Al might change the properties of minerals and consequently affect sorption behaviors of pollutants with polar functional groups (e.g., diclofenac (DCF)). In this study, batch experiments and microscale characterization were conducted to investigate the DCF sorption mechanisms to goethite and Al-substituted minerals. Goethite and Al-substituted products (including Al-goethite, Al-goethite-hematite, and Al-hematite) were synthesized with different Al contents (i.e., 0%, 5%, 10%, and 15% (in mol)) by co-precipitation method. Due to difference of ionic radius between Al and Fe and formation of excessive -OH, Al substitution resulted in deviation of cell parameters from the Vegard line. Al substitution caused increasing -OH in Al-goethite and phase transformation caused decreasing -OH in Al-hematite. The total -OH in minerals was positively related to DCF sorption capacity. In the lower initial concentration range (0.4-9 mg/L), the sorption distribution coefficient (Kd) values of goethite, Al-goethite, and Al-hematite were 21.98, 22.25, and 21.18 L/kg, respectively. Desorption characteristics and ion strength effects indicated that DCF sorption to minerals occurred mainly through outer-sphere complexation. Fourier transform infrared analyses revealed that H-bonds could be formed through -OH of minerals and -COOH of DCF, and the H-bond strength on Al-hematite was stronger than that on goethite/Al-goethite. In the normal environmental pH (e.g., 6.0 to 8.0), Kd values of DCF decreased linearly with increasing pH. These findings are helpful for understanding of DCF migration in environment involving Al-substituted minerals. © 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.