This paper examines a rapid repair material for cement concrete pavement based on magnesium phosphate cement (MPC) blended with fly ash (FA). Three kinds of stress forms for rapid repair of Portland cement concrete pavement (PCCP) were evaluated and the role of FA in the repair interface was studied. The optimal mixture ratio of FA-MPC mortar was determined, and the compressive and flexural strength tested. The composite specimens were then designed to test the interfacial bonding, tensile, and plain shear strength. Finally, the multi-scale mechanism of FA in the interface was analyzed by a pull-off adhesion test, nanoindentation test, scanning electron microscope (SEM)/energy dispersive spectrometer (EDS), Raman spectrum, and molecular dynamics simulation. The optimal content of FA in MPC mortar was 20%. The laminated beam structure had the maximum strength, and the interface load bearing capacity was the lowest. For further multi-scale analysis, the results of the pull-off adhesion test showed the adhesion strength of interface was increased by the curing age and loading rate. Adhesion capacity of basalt aggregate and FA-MPC was stronger than that of Portland cement mortar and FA-MPC. The elastic modulus of MPC-aggregate interface was more than that of MPC-OPC mortar. SEM/EDS and Raman spectrum results showed that the MPC blended with FA had cracks and defects at the interface formed with cement mortar. Less FA formed near the interface. The good adhesion ability of FA and basalt aggregate was verified by molecular dynamics simulation. By contrast, poor adhesion strength with cement mortar was confirmed.