Fiber-reinforced polymer (FRP) bar-reinforced unsaturated polyester resin concrete (UPC) can solve the problem of rebar corrosion in ordinary reinforced concrete members. However, it has not been widely used in engineering practice because there have been few studies conducted on the bond behaviors of FRP bar and UPC, and the interaction mechanisms between FRP bar and UPC have not been well understood. A series of pull-out tests are conducted on FRP bar-UPC specimens to study the bond behaviors between these two materials. Parametric studies are also carried out to investigate the effects of FRP bar diameter, fiber type, type of surface treatment, concrete cover thickness, and interfacial bond length between the two. Three failure modes of the specimens are observed from pull-out tests, i.e., FRP bar pull-out, tensile failure of FRP bar, and UPC split. A new constitutive model is, therefore, proposed to predict the bond stress of FRP bar and UPC in the residual stage, and the proposed model is finally verified by test data reported in this study.