We present a programme of characterizing Ramsey classes of structures by a combination of the model theory and combinatorics. In particular, we relate the classification programme of countable homogeneous structures (of Lachlan and Cherlin) to the classification of Ramsey classes. As particular instances of this approach we characterize all Ramsey classes of graphs, tournaments and partial ordered sets. We fully characterize all monotone Ramsey classes of relational systems (of any type). We also carefully discuss the role of (admissible) orderings which lead to a new classification of Ramsey properties by means of classes of order-invariant objects.