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Additional steel supporting joists (ASSJs) can effectively enhance the anti-overturning capacity of the existing solo-column concrete pier (SCP) bridges. Although the interface consists of bolt connections between steel and concrete is the crucial load-transmitting portion, the design of the interface between the ASSJ and SCP still mainly relies on practical experiences. In an actual bridge rehabilitation project with ASSJs in China, a novel connection comprising large-diameter bolts and an epoxy resin layer was adopted to overcome the shortcomings of the initial design. In this study, connections composited with large-diameter bolts and different interfacial treatments were investigated. Four push-out tests on the interfacial shear performance of steel–concrete connections were carried out. The experimental parameters encompassed the interface treatment method (barely roughened surface, smearing epoxy resin, and filling epoxy mortar) and the number of bolts (single row and double rows). The failure modes were unveiled. According to the experimental results, the interfacial treatment method with filling epoxy mortar could uniformly transfer stress between concrete and steel and improve the shear stiffness and shear resistance of the steel–concrete connections. Compared with specimens with barely roughened interfaces, epoxy mortar and epoxy resin employed at the steel–concrete interface can increase the shear-bearing capacity of connections by approximately 47.71% and 43.46%, respectively. However, the interfacial treatment method with smearing epoxy resin resulted in excessive stiffness of the shear members and brittle failure mode. As the number of the bolts increased from a single row to a double row, the shear-bearing capacity of a single bolt in the specimen exhibited approximately an 8% reduction. In addition, by comparing several theoretical formulae with experimental results, the accurate formula for predicting the shear-bearing capacity of bolts was recommended. Furthermore, the load-bearing capacity of an ASSJ in the actual engineering rehabilitation was verified by the recommended formula GB50017-2017, which was found to accurately predict the shear-bearing capacity of large-diameter bolt connectors with an epoxy mortar layer. Full article