With mastery over the colloidal synthesis of monometallic nanocrystals, a combination of two distinct metals with intricate architectures has emerged as a new direction of innovation. Among the diverse architectures, the one with a core–shell structure has attracted the most scientific endeavors owing to its merits of high controllability and variability. Along with the new hopes arising from the addition of a shell composed of a different metal, there comes unexpected complications for the surface composition, hindering both structural understanding and application performance. In this Focus article, we present a brief overview of the opportunities provided by the bimetallic core–shell nanocrystals, followed by a discussion of the technical challenge to elucidate the true composition of the outermost surface. Some of the promising solutions are then highlighted as well, aiming to inspire future efforts toward this frontier of research.