Abstract. This is the first of a series of papers devoted to certain pairs of commuting nilpotent elements in a semisimple Lie algebra that enjoy quite remarkable properties and which are expected to play a major role in Representation theory. The properties of these pairs and their role is similar to those of the principal nilpotents. To any principal nilpotent pair we associate a two-parameter analogue of the Kostant partition function, and propose the corresponding two-parameter analogue of the weight multiplicity formula.In a different direction, each principal nilpotent pair gives rise to a harmonic polynomial on the Cartesian square of the Cartan subalgebra, that transforms under an irreducible representation of the Weyl group. In the special case of sl n , the conjugacy classes of principal nilpotent pairs and the irreducible representations of the Symmetric group, S n , are both parametrised (in a compatible way) by Young diagrams. In general, our theory provides a natural generalization to arbitrary Weyl groups of the classical construction of simple S n -modules in terms of Young's symmetrisers.First results towards a complete classification of all principal nilpotent pairs in a simple Lie algebra are presented at the end of this paper in an Appendix, written by A. Elashvili and D. Panyushev.