A novel process for solidification/stabilization of EMR and simultaneous reusing it as resource was proposed. A new type of photocatalytic cement materials (TiO2-EMR cement) was developed by coating TiO2 onto EMR-cement. The sol–gel dip-coating method was investigated to prepare the TiO2-EMR cement materials. Degradation of methyl orange (MO) was selected to assess the self-cleaning activity of the cement samples. The influence of calcination temperature, coating cycles, leaching property, especially utilization cycles was systematically investigated. The results indicated that the maximum MO degradation of 94.2% was achieved. Furthermore, the photocatalytic activity of the cement coated with TiO2 can be regenerated by calcination at 500 °C for 2 h and used repeatedly. In addition, leaching toxicity of the prepared cement can meet the national standards. Therefore, the results obtained in this study established a technical suitability of reuse electrolytic manganese residue as raw material for self-cleaning cement materials.