Using a monomeric and two polymeric coupling agents, interfacial aspects of electrodeposited (ED) carbon fiber/epoxy composites were investigated by means of fragmentation techniques and acoustic emission (AE). ED results for dipped and untreated fibers under dry and wet conditions were compared. Multifiber-embedded composites (MFC) were prepared for direct comparison. Various treating conditions such as treating time, concentration of coupling agent, and treating temperature were optimized, respectively. The adsorption mechanisms of the coupling agents onto the carbon fiber were analyzed in terms of the electrolyte molecular interactions during ED process, due to chain mobility in the aqueous solution. The microfailure mechanisms occurring from fiber breaks, and matrix and interlayer cracks were examined by AE parameters. The interfacial shear strength (IFSS) of ED-treated carbon fibers was much higher than that of the other two cases under dry and wet conditions. Well-separated AE groups were found for the untreated, the dipped, and the ED-treated cases, and significantly more AE events occurred from the ED interlayer failure between fiber and matrix than from the untreated and even than from the dipping cases. AE events from different-type interlayers may be correlated with IFSS based on the differing mechanical and chemical roles of the interlayers.