The alignment of atoms with inner-shell vacancies resulting from ionization by photons was investigated by measuring the anisotropic emission of L shell X-ray lines. The X-ray line intensities were measured using an Si(Li) detector and radioisotope photon source in various emission angles. It was observed from measured intensities that L alpha and Ll X-ray intensities for the L-3 sub-state depended on the emission angle, meaning that L alpha and Ll X-rays had an anisotropic spatial distribution. Thus, the L alpha to Ll intensity ratios for a set of elements were determined and alignment parameters for each element were obtained using these ratios. Also, the empirical values of the L-3 magnetic sub-state photoionization cross-sections for m(j) = 3/2 and 1/2 were evaluated using the determined alignment parameters, sub-state photoionization cross-sections and the Coster-Kronig transition probabilities. (C) 2009 Elsevier Ltd. All rights reserved.