The polymer cement mortar (PCM) overlay method is a promising solution for strengthening deteriorated concrete structures in which the occurrence of premature debonding at the interfaces prevents the strengthened structures from achieving full serviceability. The purpose of this study is to improve the concrete–PCM interfacial bond to prevent premature debonding. There are two main focuses of this study: (i) investigation of the effectiveness of adding 5% silica fume to PCM in forming a chemical connection between concrete and PCM, based on a direct single-surface shear test using two roughness levels of concrete (smooth and rough) and microstructure analysis and (ii) performance evaluation of the bond between substrate concrete and a PCM overlay with/without silica fume at early ages and with different moisture conditions at the interface, based on a bi-surface shear test using rough substrate concrete surface. The inclusion of 5% silica fume with PCM caused an improvement in the interfacial strength (approximately 113% relative to the normal PCM in cases of without primer), with a smooth concrete substrate surface where mechanical bonding had less influence. In addition, lower Ca/Si values in the interface of modified 5% silica PCM specimens compared to the normal PCM specimens quantified by energy-dispersive X-ray spectroscopy (EDS) indicate the formation of a chemical connection at the concrete–PCM interface by transforming harmful Ca(OH)2 into more C-S-H which strongly improves the bonding strength. As a repair layer mortar, the positive influence of silica fume in modified 5% silica PCM specimens was also found at early ages and with different moisture conditions at the interface compared to the normal PCM. In conclusion, the addition of silica fume to the PCM caused chemical connection at the concrete–PCM interface and improved the interfacial performance.