By electrodeposition (ED) using a monomeric- and two polymeric coupling agents, the interfacial shear strength (IFSS) of carbon fiber/epoxy composites was investigated by fragmentation test. ED results were compared with the dipping and the untreated cases under dry and wet conditions. Multi-fiber composites (MFC) were used for the direct comparison for the untreated and the treated cases. Various treating conditions including time, concentration and temperature were evaluated, respectively. Under dry and wet conditions ED treatment exhibited much higher IFSS improvement compared to the dipping and the untreated cases. Monomeric- and polymeric coupling agents exhibited the comparative IFSS improvement. Adsorption mechanism between coupling agents and carbon fiber was analyzed in terms of the electrolyte molecular interactions during ED process based on to the chain mobility. The microfailure modes occurring from the fiber break, matrix and interlayer cracks were correlated to IFSS.