This work reported a process for the preparation of Portland cement clinker from sulfuric acid leaching residue of coal fly ash. Aluminum and iron in fly ash were effectively leached by sulfuric acid leaching, and the silica was all concentrated in the acid leaching residue. The chemical analysis showed that the content of SiO2 in the leaching residue was 79.1% and the leaching residue contained a small amount of Al2O3, CaO and Fe2O3, which could replace clay as the raw material for the preparation of Portland cement clinker. The effects of main process conditions on the quality of prepared cement clinker were studied. The results showed that the burnability of the raw material with clinker rate value KH = 0.92, SM = 2.1, IM = 1.2 and leaching residue content of 26.98% was excellent and good. The mineralogical analysis and microscopic examination showed that the good quality clinker was obtained under the conditions of sintering temperature of 1450 °C and holding time of 60 min, and the tricalcium silicate phase was well developed. Based on this study, acid leaching residue of coal fly ash was viable as an effective, alternative raw material in Portland cement production.