This research investigated whether subjects with Alzheimer's disease (AD) and ischaemic vascular dementia (IVD) associated with periventricular and deep white matter alterations can be dissociated on tests of declarative and procedural memory, as well as on MRI indices of white matter alterations and the size of the hippocampal formation. The California Verbal Learning Test (CVLT) and the Pursuit Rotor Learning Tests (PRLT) were used to measure declarative and procedural memory, respectively. Subjects with IVD obtained a higher score on the CVLT recognition discriminability index; however, on the PRLT total time on target, carry-over between trial blocks, and slope calculated for all test trials was low. Subjects with AD exhibited the opposite profile. MRI studies indicated that subjects with IVD had considerably greater white matter alterations, but larger hippocampal formations than subjects with AD. Higher scores on the CVLT recognition discriminability index were correlated with increased size of the body of the hippocampus and parahippocampal gyrus. By contrast, as the severity of white matter alterations increased the slope on the PRLT declined. In sum, subjects with AD and IVD can be dissociated on the basis of differing patterns of impairment on tests of declarative and procedural memory, and MRI indices of white matter alteration and the integrity of the hippocampal formation.