We explore two- or three-class association schemes. We study aspects of the structure of the relation graphs in association schemes which are not easily revealed by their parameters and spectra. The purpose is to develop some combinatorial methods to characterize the graphs and classify the association schemes, and also to delve deeply into several specific classification problems. We work with several combinatorial objects, including strongly regular graphs, distance-regular graphs, the desarguesian complete set of mutually orthogonal Latin squares, orthogonal arrays, and symmetric Bush-type Hadamard matrices, all of which give rise to many small-class association schemes. We work within the framework of the theory of association schemes.;Our focus is placed on the search for all isomorphism classes of association schemes and characterization of small-class association schemes of specific order. In particular, we examine two-class association schemes (strongly regular graphs) of order 64 and their three-class fission schemes. After we collect 'feasible' parameter sets for the putative association schemes, we make an attempt to check the realization (existence) of the parameter sets and describe the structure of the schemes chiefly by investigating the structure of their relation graphs. In the course of this thesis, we find a new way to construct orthogonal arrays and investigate their implications for strongly regular graphs, symmetric Bush-type Hadamard matrices, and three-class association schemes. We obtain several results regarding the characterization and classification of two- or three-class association schemes of order 64.