A new method for increasing the interface resistance between geopolymer coating and concrete lining structure without applying the organic binder was suggested in this study. Parallel grooves with different depths and orientations were milled on the top surface of concrete block, and well-blended geopolymer mixture (Na-PSS type geopolymer: Sodium poly-sialate-siloxo) was coated upon the grooved interface. The wedge splitting (WS) experiments were conducted to compare the interface adhesion capacity of specimens with different groove width/depth ratios and groove orientations. The average energy release rate (ERR) was calculated by integrating the Pv-CMOD diagram to quantify the interfacial fracture toughness. To understand the interface strength mechanisms and the fracture mode at the front crack mouth, franc 3D simulation was carried out to segregate the mixed fracture mode to determine the initial pure stress intensity factors at the crack mouth. Both the experiments and simulation results indicated that the highest interface fracture toughness was reached by the double diagonal parallel grooves with 0.375 width/depth ratio. These findings put forward a promising attaching method for efficient and reliable passive fire protection coating, with the aim of decreasing the risk of layer delamination in highway tunnels.