Statistical inference on graphs often proceeds via spectral methods involving low-dimensional embeddings of matrix-valued graph representations such as the graph Laplacian or adjacency matrix. In this paper, we analyze the asymptotic information-theoretic relative performance of Laplacian spectral embedding and adjacency spectral embedding for block assignment recovery in stochastic blockmodel graphs by way of Chernoff information. We investigate the relationship between spectral embedding performance and underlying network structure (e.g., homogeneity, affinity, core-periphery, and (un)balancedness) via a comprehensive treatment of the two-block stochastic blockmodel and the class of K-blockmodels exhibiting homogeneous balanced affinity structure. Our findings support the claim that, for a particular notion of sparsity, loosely speaking, “Laplacian spectral embedding favors relatively sparse graphs, whereas adjacency spectral embedding favors not-too-sparse graphs.” We also provide evidence in support of the claim that “adjacency spectral embedding favors core-periphery network structure.”