With ER2319 and B4C powder as feedstocks and additives, respectively, a wire arc additive manufacturing (WAAM) system based on double-pulse melting electrode inert gas shielded welding (DP-MIG) was used to fabricate single-pass multilayer 2319 aluminum alloy. The results showed that, compared with additive manufacturing component without B4C, the addition of which can effectively reduce the grain size (from 43 μm to 25 μm) of the tissue in the deposited layer area and improve its mechanical properties (from 231 MPa to 286 MPa). Meanwhile, the mechanical properties are better in the transverse than in the longitudinal direction. Moreover, the strengthening mechanism of B4C on the mechanical properties of aluminum alloy additive manufacturing mainly includes dispersion strengthening from fine and uniform B4C granular reinforcing phases and fine grain strengthening from the grain refinement of B4C. These findings shed light on the B4C induced grain refinement mechanism and improvement of WAAM 2319 Al alloy.