The synthesis of highly uniform alloy nanocrystals with a concave feature is desirable for applications in catalysis but is an arduous task. This article proposes an initiative protocol for the fabrication of novel Cu-Pd alloy nanocrystals, wherein the volume of decylamine (DA) in the reaction system was found to greatly influence the formation of different morphologies, including the tetrahedron (TH), concave tetrahedron (CTH), rhombohedral-tetrapod (RTP), and tetrapod (TP). The alloy structure of the products arises from the coordination interaction between the DA and metal ions, which affects the reduction potential of Cu and Pd species, and thus yields co-reduction. Other reaction parameters, such as the type of ligand, amount of reductant, and temperature, were also altered to study the growth mechanism, yielding consistent conclusions in the diffusion-controlled regime. As a catalyst, 48-nm Cu-Pd concave tetrahedral nanocrystals were highly active for the hydrogenation of 3-nitrostyrene and exhibited > 99.9% chemoselectivity to C=C instead of -NO₂.