Because of the strong alkalinity of red mud, it is difficult to recycle, and the long-term accumulation of red mud causes environmental pollution. The study shows that the solidification characteristics of bayer red mud (RM) under the action of Ca(OH)2 (CH) are obvious. The mechanical properties of Bayer RM paste with different amounts of CH at different ages were tested. The strength of RMCH gradually increases with the increase in CH content and age, reaching a turning point in strength at 26.4% content of CH, with the highest strength at 28 days, reaching 2.73 MPa. The solidification products were characterized by XRD, FTIR, TG-DTG, and SEM-EDS. The results show that under the action of CH, the main solidification products of RM are C-(A)-S-H, hemicarboaluminate, and monocarboaluminate. In the solidification process, hydroxysodalite and faujasite-Na react with CH to generate C-S-H, Al(OH)4−, and Na+, then react to generate hemicarboaluminate, monocarboaluminate and C-(A)-S-H, among which hemicarboaluminate is transformed into monocarboaluminate in the presence of calcite, and further monocarboaluminate decomposes to generate calcite. It provides a basis for the study of the interaction mechanism between a single substance and RM and provides a research basis for the sustainable utilization of red mud.