A distance based on the exponential kernel of the adjacency matrix of a graph and representing how well two vertices connect to each other in a graph is defined and studied. This communicability cosine distance (CCD) is a Euclidean spherical distance accounting for the cosine of the angles spanned by the position vectors of the graph vertices in this space. The Euclidean distance matrix (EDM) of CCD is used to quantify the similarity between vertices in graphs and networks as well as to define a local vertex invariant—a closeness centrality measure, which discriminate very well vertices in small graphs. It allows to distinguish all nonidentical vertices, also characterizing all identity (asymmetric) graphs–those having only the identity automorphism–among all connected graphs of up to 9 vertices. It also characterizes several other classes of identity graphs. We also study real-world networks in term of both the discriminating power of the new centrality on their vertices as well as in ranking their vertices. We analyze some dictionary networks as well as the network of copurshasing of political books, remarking some of the main advantages of the new approaches studied here.