In order to study the failure mode and debonding behavior of the interface between BFRP (basalt fiber reinforced polymer) sheet and structural steel under mixed-mode loading conditions, eighteen specimens with different initial angles were tested in this study. The specimens were designed with different initial angles to ensure that the interface performed under mixed-mode loading conditions. The relations between the bond strengths, failure modes, and initial angles were investigated. A new evaluation method to predict the interfacial bond strength under shear-peeling loading mode was proposed. The test results show that specimens with a smaller initial angle are more likely to exhibit a shear debonding failure at the interface between the steel plate and adhesive. In contrast, specimens with a larger initial angle are more likely to exhibit peeling of the interface. The ultimate tensile strength of the specimen is higher with a smaller initial angle. The results predicted by the proposed method are in good agreement with the experimental results.