In recent years, ecology conservation optimization (ECO) modified polyurethane concrete is becoming popular in steel deck pavement areas. However, it is reported that the interface performance between steel and ECO concrete suffers a significant degradation caused by diurnal and seasonal thermal cycling. In this paper, the interfacial performance of steel and ECO concrete composites at different temperatures was investigated through four groups of oblique tests at the temperature of −10 °C, 15 °C, 40 °C and 60 °C. The digital image correlation (DIC) technique is used to measure the strain distribution. The results show that the interfacial shear strength and stiffness of the specimens decrease with the growth of temperature, while the ultimate relative slip increases. Based on regression analysis, the formulas for calculating the interfacial shear strength, shear stiffness, and ultimate relative slip of steel and ECO concrete composites at different temperatures were established. A temperature dependent bond-slip constitutive model was proposed then by considering the temperature dependency of model parameters, which shows great accuracy in describing the bond-slip behavior between the steel and ECO concrete. Furthermore, a finite element analysis (FEA) model was established based on cohesive behavior, which agrees well with experimental results. Our research results can provide guidance for engineering applications of ECO concrete.