strength, [7] while weakening the interphase can produce additional toughness via fiber debonding and plastic deformation of the interfacial layer. [8] Therefore, engineering the interphase so as to solve the conflict between strength and toughness affords a good opportunity.Nacre, a unique microscale architecture of "brick-and -mortar" that can reform after breaking, endows it with pre-eminent mechanical strength and toughness. [9] Thus, considerable attentions have been contributed to mimic this delicate structure, aiming at gaining exceptional mechanical properties. Different inorganic materials, including graphene, [10] layered double hydroxide (LDH), [11] nanoclay, [12] man-made CaCO 3 , [13] Al 2 O 3 , [14] carbon nanotube (CNT), [15] and TiO 2 , [16] have been employed as "bricks" in fabrication of analogous nacre film materials. Observation of these nacre-like films indicates that the introduction of adequate reinforcing components and appropriate interfacial interactions over several distinct scales are keys affecting the mechanical properties. Inspired by these, whether construction of an composite interphase with nacre-like layered structure can simultaneously enhance the composites' interfacial strength and toughness?Layer-by-layer (LbL) assembly provides a good approach to fabricate such nacre-like layered structure at interphase region, since it has been proved to be a facile way for the fabrication of hierarchical nanostructured layers on various substrates via electrostatic interaction between differently charged materials. [1,6,17] To manifest the critical characteristics of natural nacre, a LDH/poly(sodium-4-styrenesulfonate) nanostructured coating over the surface of glass fiber by LbL was reported by Luca et al., [8] which increased the interfacial shear strength (IFSS) and debonding toughness by 30% and 162%. In addition, the LbL method has been employed to deposit graphene oxide (GO)/aramid nanofiber multilayers, [18] GO/SiO 2 multilayers, [19] and CNT coatings [20] on glass fiber or carbon fiber surface to improve interfacial adhesion of composites.Polydopamine (PDA) and other catechol compounds, due to their outstanding adhesive property and the role of providing platform for secondary reactions, are highly sought after being used to modify the inert surface of carbon fibers. [21][22][23][24][25] Moreover, PDA has dense aromatic structures in its molecular Interphase with nacre-like structured multilayer is constructed by alternatively depositing two polymers, respectively "rigid" polydopamine (PDA) and "flexible" polyether amine, on carbon fiber surface via the layer-by-layer (LbL) approach. The optimal interfacial strength and toughness are achieved for composites with three layers of PDA/polyether amine, respectively, 39.2% and 99.8% superior to the untreated fiber composites. The outstanding mechanical properties are mainly ascribed to the synergistic interactions of covalent bond, hydrogen bonding, and π-π stacking among fiber, multilayer, and matrix by transferring stress and bridgin...