The interface performance between clay–sand mixtures and concrete structures is governed by the mixture's composition and its physical properties. Moisture content and particle-size distribution play important roles in deciding the mixture's arrangement of soil particles, porosity, hydraulic conductivity and behaviour under various mechanical loadings. Application of a polymer interfacial coating can improve the bond performance between soils and concrete mainly via interfacial friction/mechanical interlocking. The present work analyses the development of interfacial strength between clay–sand mixtures and a polymer coating with changes in particle gradation. The multi-scale mechanisms at the interface are investigated, giving primary attention to soil porosity. A 50:50 clay–sand mixture exhibited a greater interfacial adhesive performance compared to other soil mixtures. In addition, the moisture-controlled pores and gradation-controlled pores demonstrated differences in macroscale interfacial strength. Both mercury intrusion porosimetry (MIP) and 129Xe nuclear magnetic resonance (NMR) were utilized to detect the pore structure of the mixtures. 129Xe-NMR revealed the pore distribution of the mixtures as ranging from macropores to nanopores, and MIP complemented the pore information by determining the critical pore entry diameter in the macropore regime. Mesopores dominated with increasing fine sand content until a threshold value was reached; thereafter, merging of pores occurred and macropores dominated.