The correspondence between weighted undirected graphs and reversible Markov chains via vertex random walks is simple and well known. Leveraging this correspondence and ideas from the theory of dynamical systems, we study the structural discordance of graphs and Markov chains by means of graph joinings. Informally, a joining of graphs $G$ and $H$ is a graph on the product of their vertex sets giving rise to a coupling of their random walks. Graphs $G$ and $H$ are strongly disjoint if their only joining is the tensor product, and they are weakly disjoint if the degree function of every joining is equal to the degree function of the tensor product. We establish close connections between graph joinings, disjointness, and graph factors. Our first principal result characterizes weak disjointness of graphs in terms of the spectral overlap of their Markov transition matrices. The second establishes that two graphs without self loops are strongly disjoint if and only if they are weakly disjoint and exactly one of the graphs is a tree. The third shows that the strong or weak disjointness of graphs is essentially determined by their vertex and edge sets, without regard to edge weights. Translating these results into the language of Markov chains yields new insights into the rigidity and structure of reversible couplings of reversible Markov chains.