An Al–Cu matrix composite reinforced with uniformly-distributed micron- and nano-double-sized TiC particles (MNDS-TiCps) was successfully fabricated using a wire and arc additive manufacturing (WAAM) process. The combined effect of the MNDS-TiCps on the precipitation of the θ″ phase, the structural evolution of the grain boundaries, and solidification dynamics of the deposited Al–Cu matrix composites were subsequently investigated. The micron-sized TiC particles in the molten pool generate nucleation undercooling (ΔTnu, ∼0.32 K) which inhibits grain boundary segregation due to constitutional undercooling and promotes the redistribution of the Cu solute in the Al matrix. The phase composition at the grain boundaries changes from θ-Al2Cu to α-Al + θ-Al2Cu and the non-coherent interface between the α+θ transition zone and θ grain boundary is transformed into a coherent interface between the α+θ grain boundary and Al matrix, i.e. (211)θ-Al2Cu//(111)Al. The decrease in free energy within the Al matrix provides energy to facilitate the growth of nuclei on the surface of the nano-sized particles. A semi-coherent interface is thus detected between the TiC and precipitates, characterized by a crystal orientation relationship of (200)TiC//(310)θ″-Al2Cu. The dislocations that provide pipe-diffusion paths for solute Cu constitute a driving force that coarsens the precipitates, promoting the precipitation of θ″ precipitates. Multi-site co-deformation combined with dislocation increment inhibits stress damage to the micro-interface. The strength and elongation increase by 51.0 % and 118 %, respectively, compared to specimens without TiC. This work provides a novel perspective for tailoring WAAM-deposited Al–Cu alloys by achieving favorable structural evolution in the grain boundaries, inducing the precipitation of precipitates, and yielding outstanding synergy between ductility and strength.