Steinerberger defined a notion of boundary for a graph and established a corresponding isoperimetric inquality. Hence, "large" graphs have more boundary vertices. In this paper, we first characterize graphs with three boundary vertices in terms of two infinite families of graphs. We then completely characterize graphs with four boundary vertices in terms of eight families of graphs, five of which are infinite. This parallels earlier work by Hasegawa and Saito as well as Müller, Pór, and Sereni on another notion of boundary defined by Chartrand, Erwin, Johns, and Zhang.