In this work, a high ferrite Portland cement clinker was synthesized at high temperature using solid waste, and the doping mechanism of sodium (Na) in the main clinker phases was studied. The results showed that the main mineral phases of solid waste based high ferrite Portland cement clinker are 68.3% β-C2S, 21.0% C4AF, 6.6% C3A, and a small amount of C3S, the compressive strength at 28 days with an 8% desulfurization gypsum content is 16.7 MPa; Na is easily dissolved in the ferrite and tends to replace Ca2+, but it is difficult to dissolve in the C2S, especially in replacing Si; Except for Si, Na atoms form the same coordination number with host atoms (Al, Fe, and Ca), only causing local structural distortion, which is reflected in local bonding structures rather than overall crystal deformation.