This is the first book to comprehensively cover quantum probabilistic approach to spectral analysis of graphs. This approach was initiated by the authors and has become an interesting research area in applied mathematics and physics. The text offers a concise introduction to quantum probability from an algebraic perspective. Topics discussed along the way include quantum probability and orthogonal polynomials, asymptotic spectral theory (quantum central limit theorems) for adjacency matrices, method of quantum decomposition, notions of independence and structure of graphs, and asymptotic representation theory of the symmetric groups. Readers will learn several powerful methods and techniques of wide applicability, recently developed under the name of quantum probability. End-of-chapter exercises promote deeper understanding.