The interface of fresh-aged concrete represents a critical vulnerability within monolithic assembled monolithic concrete structures. In this paper, the shear performance of the interface between post-cast epoxy resin concrete and standard concrete is studied using experimental methods and finite element analysis. The objective is to furnish empirical data that support the broader adoption of epoxy resin concrete in assembled structures. A direct shear experiment of 19 Z-shaped samples and a computation of 20 finite element models were completed. The results from both experimental and computational analyses provided insights into several factors influencing the shear performance at the interface. These factors include the pre-cast part of concrete strength, the friction coefficient of the interface, the longitudinal reinforcement ratio at the interface, the compressive strength of concrete in the post-cast part, and confining stress. The findings indicate that utilizing epoxy resin concrete for post-cast material, roughing the interface, and setting keyways can enhance the shear performance of the interface so that it equals or even exceeds the cast-in situ sample. Optimal shear results are obtained when the compressive strength of the post-cast epoxy resin concrete closely matches that of the pre-cast conventional cement. Moreover, increasing the depth of the keyways rather than their width is more effective in improving the shear capacity of the sample. It is recommended that the depth of the keyway should be at least 30 mm, and its width should be no less than three times the depth. As the longitudinal reinforcement ratio at the interface increases, there is an enhancement in shear capacity coupled with a reduction in deformative performance. It is advisable to maintain this ratio below 1.0% to balance the strength and ductility effectively.