Methods are developed for structural analysis of metabolic networks expanding in size. Expansion proceeds in consecutive generations in which new reactions are attached to the network produced in the previous stage. Different rules are applied resulting in various modes of expansion. Expansion is performed on the set of glycolytic reactions as well as on a very large set of reactions taken from the KEGG database. It is shown that reactions and compounds strongly differ in the generation in which they are attached to the network allowing conclusions for the temporal order of the acquisition during network evolution. The expansion provides efficient tools for detecting new structural characteristics such as substrate-product relationships over long distances.