The direct-to-blister smelting process realizes single furnace smelting from chalcocite to blister copper. This process saves the matte transport process, avoids multiple feeding in the smelting process, and has the advantages of high productivity, a short production process, and less SO2 pollution. By comparing with the phase diagram of iron silicate slag system, it shows that calcium ferrite slag system is more suitable for direct-to-blister smelting under the condition of high oxygen potential. In this study, high-grade copper concentrate was used as the raw material and direct-to-blister smelting experiments were carried out at the laboratory scale. The variation of copper recovery with CaO/Fe ratio, smelting temperature and sedimentation time was studied. The phase composition of slag and the loss of copper in slag were analyzed by X-ray diffraction (XRD) and scanning electron microscopy with an energy spectrometer (SEM-EDS). The results showed that by adjusting process parameters, the copper recovery can reach 90.15 wt.% and the blister copper grade is more than 98.50 wt.%. It provides a theoretical basis for the industrial application of calcium ferrite slag in direct-to-blister smelting.