The conversion mechanism of Al-goethite under the action of different additives (lime or reductant for typical or reductive Bayer digestion) was investigated by thermodynamic calculation, XRD, and SEM-EDS. The results show that the formation of Fe-substituted hydrocalumite is crucial to converting Al-goethite to hematite during Bayer digestion by adding lime. However, the conversion proceeds more easily under the action of reductant due to the rapid formation of magnetite. Additionally, Bayer liquor composition significantly affects the product composition and also the conversion rate of Al-goethite. Compared to typical Bayer digestion with Al-goethite containing gibbsitic bauxite as raw material, the red mud yield of reductive Bayer digestion decreases from 39.02% to 31.19%, and the grade of TFe in red mud increases from 41.66% to 53.80%.