Interfacial and microfailure properties of carbon fiber/epoxy composites were evaluated using both tensile fragmentation and compressive Broutman tests. A monomeric and two polymeric coupling agents were applied via the electrodeposition (ED) and the dipping applications. A monomeric and a polymeric coupling agent showed significant and comparable improvements in interfacial shear strength (IFSS) compared to the untreated case under both tensile and compressive tests. Typical microfailure modes including cone-shaped fiber break, matrix cracking, and partial interlayer failure were observed under tension, whereas the diagonal slipped failure at both ends of the fractured fiber appeared under compression. Adsorption and shear displacement mechanisms at the interface were described in terms of electrical attraction and primary and secondary bonding forces.