To investigate the effect of NiCrTi coating on the ash condensation characteristics of high-alkali coal in Xinjiang South Mine, we first built an experimental rig for high-alkali-coal flue gas condensation and carried out experimental research on high-alkali-coal flue gas condensation. Physicochemical characterization of the initial layer of the ash deposit (initial deposit) condensation products was also carried out using XRD, SEM, and EDX. Finally, the priority of products generated on the surface of NiCrTi coating and the three-phase diagram of Na2O-SiO2-Al2O3 were analyzed by using FactSage 8.3 thermodynamic software. The results show that the condensation products in the initial deposits layer of 15CrMo alloy contain other sodium salts, such as sodium feldspar (NaAlSi3O8), NaCl, and Na2SO4, and that other protective oxides, such as Cr2O3, NiCr2O4, and TiO2, are formed on the surface of the NiCrTi coating. At the same time, the condensation experiment allows the fouling phase to be divided into four parts. Secondly, it was found that the densely flaky particles on the surface of NiCrTi coatings not only have excellent anti-fouling properties but also can effectively inhibit the penetration of other elements such as S. Finally, the reaction priority of protective oxides on NiCrTi coatings was calculated by FactSage 8.3 and found to have the following order: NiCr2O4 > Cr2O3 > TiO2. The results of this paper provide theoretical support for the development of anti-staining NiCrTi coatings.