This book is dedicated to the structure and combinatorics of classical Hopf algebras. Its main focus is on commutative and cocommutative Hopf algebras, such as algebras of representative functions on groups and enveloping algebras of Lie algebras, as explored in the works of Borel, Cartier, Hopf and others in the 1940s and 50s. The modern and systematic treatment uses the approach of natural operations, illuminating the structure of Hopf algebras...