Glass fiber-reinforced polymer (GFRP) of high performance, as a relatively ideal partial or complete substitute for steel, could increase the possibility of adapting structures to changes in harsh weather environments. While GFRP is combined with concrete in the form of bars, the mechanical characteristics of GFRP cause the bonding behavior to differ significantly from that of steel-reinforced members. In this paper, a central pull-out test was applied, according to ACI440.3R-04, to analyze the influence of the deformation characteristics of GFRP bars on bonding failure. The bond–slip curves of the GFRP bars with different deformation coefficients exhibited distinct four-stage processes. Increasing the deformation coefficient of the GFRP bars is able to significantly improve the bond strength between the GFRP bars and the concrete. However, while both the deformation coefficient and concrete strength of the GFRP bars were increased, the bond failure mode of the composite member was more likely to be changed from ductile to brittle. The results show members with larger deformation coefficients and moderate concrete grades, which generally have excellent mechanical and engineering properties. By comparing with the existing bond and slip constitutive models, it was found that the proposed curve prediction model was able to well match the engineering performance of GFRP bars with different deformation coefficients. Meanwhile, due to its high practicality, a four-fold model characterizing representative stress for the bond–slip behavior was recommended in order to predict the performance of the GFRP bars.