We study the canonical complexifications of non-compact Riemannian symmetric spaces by the Grauert tube construction. We determine the maximal such complexification, a domain already constructed by Akhiezer and Gindikin [1], and show that this domain is Stein. We also determine when invariant complexifications, including the maximal one, are Hermitian symmetric. This is expressed simply in terms of the ranks of the symmetric spaces involved.