Alignment of M-subshell vacancy states after photoionization in Pb by 5.959 keV photons has been reported. The present results contradict the predictions of Cooper and Zare that, after photoionization of inner shells, the vacancy state has equal population of magnetic substates and the subsequent x-ray emission is isotropic, but confirm the predictions of the calculations of Flugge, Mehlhorn and Schmidt that the atomic inner-shell vacancies produced after photoionization are aligned and the x-ray emission from the filling of vacancies in states with J > 1/2 is anisotropic.