Adsorption behavior of atomic deuterium on a hexagonal boron nitride (h-BN) thin film is studied by photon-stimulated ion desorption (PSID) of D(+) and near edge X-ray absorption fine structure (NEXAFS) at the B and N K-edges. After the adsorption of atomic deuterium, D+ desorption yield eta(nu) shows clear enhancement at the B K-edge and almost no enhancement at the N K-edge. NEXAFS spectra show a large change in the B K-edge and a small change in the N K-edge after the adsorption. We propose selective adsorption of atomic deuterium on the h-BN thin film based on the experimental results, and mention the effectiveness of applying the PSID method with X-ray to study hydrogen storage materials. (C) 2011 Elsevier B.V. All rights reserved.