We have investigated photon-stimulated ion desorption from deuterated benzene (C6D6) adsorbed on Si(1 0 0) and Si(1 1 1) surfaces following C 1s core excitation. Using time-of-flight mass spectrometry combined with angle-dependent technique, we measured the dependences of mass-spectra of desorption ions on photon energies and on incident angle (theta) of synchrotron beam. We have found the ion yields for adsorbate-derived fragments of CD+ and CD2+ are enhanced in very small angles of incident X-rays. Moreover, molecular orientation effect appeared in excitation energy dependences of D+ ions from the Si(1 0 0) and Si(1 1 1) surfaces; that is, ion yield spectra measured at theta = 10 degrees are different from that at theta = 65 degrees. Furthermore, it was found that desorption ion yields increase greatly with decreasing incident angles. The angular dependences are consistently similar for all ion species, excitation energies, and indexes of substrates. Possible desorption processes are described on the basis of the observations. (C) 2008 Elsevier B. V. All rights reserved.