With the growing application of prefabricated building structural systems, precast concrete double-faced superposed shear wall (PCDSSW) structures have gained increasing popularity in multi-story and high-rise buildings. However, limited research on the eccentric compressive performance of PCDSSWs could lead to severe consequences. To address this issue, this study conducted eccentric load tests on seven full-scale PCDSSW specimens with steel truss connectors and one full-scale cast-in-place reference specimen. The influence of various design parameters, including truss web diameter, trusses layout, connection locations and methods between steel trusses and distribution reinforcement on the eccentric compressive performance of PCDSSWs was analyzed and discussed. The results revealed that both cast-in-place and PCDSSW specimens exhibited similar failure modes characterized by large eccentric compression failure. PCDSSW specimens showed no noticeable laminated interface separation and can achieve the design objective of "comparable performance to cast-in-place". Moreover, the diameter of truss web reinforcement and the layout of steel trusses had minimal impact on the eccentric compression performance of PCDSSW. While employing welded connections could boost the load-bearing capacity and cracking stiffness of PCDSSW, it also led to a marginally faster stiffness degradation rate and reduced deformation capacity. Additionally, the existing design standards yield conservative predictions for the load-bearing capacity of PCDSSWs. Furthermore, the model proposed by GB 50010–2010 is advocated due to its reliability and accuracy.