The cytochromes c include subgroups which present a variety of redox functions based on well-defined changes in the basic three-dimensional structure exemplified by the mitochondrial and certain bacterial forms, in particular cytochromes c2. These proteins exhibit overlapping functionality and a graded sequence of structures which provide paradigms well suited for clarification of recognition mechanisms. The character and distribution of cytochromes c will be discussed and approaches to relatedness of structure and function will be described, based on kinetic analyses of cross reactivities of cytochromes c2 with mitochondrial cytochrome c oxidase.