Modified PZT samples were poled at different voltages and the structures were analyzed with X-ray diffraction techniques. The results show that in the present studies the 90° domains were more readily aligned in the direction of poling than were the 180° domains. Explanations of these features were based on the refined structural co-ordinates of a powdered sample. Calculations of the shifts in atomic positions during domain alignment were indeed less for the 90° domain at low poling field and suggest the alignment of these domains was energetically more favourable.