We introduce post-associative algebra structures and study their relationship to post-Lie algebra structures, Rota-Baxter operators and decompositions of associative algebras and Lie algebras. We show several results on the existence of such structures. In particular we prove that there exists no post-Lie algebra structure on a pair (g, n), where n is a simple Lie algebra and g is a reductive Lie algebra, which is not isomorphic to n. We also show that there is no post-associative algebra structure on a pair (A, B) arising from a Rota-Baxter operator of B, where A is a semisimple associative algebra and B is not semisimple. The proofs use results on Rota-Baxter operators and decompositions of algebras.