The configuration of hydroxyl groups around the octahedral cations of 2:1 phyllosilicate minerals has long been an important question in clay science. In the present study, 27Al multiple quantum (MQ) magic angle spinning nuclear magnetic resonance (MAS NMR) was applied to the local structural analysis of octahedral Al positions in a purified Na-montmorillonite. Three octahedral Al sites (Ala, Alb, and Alc) are distinguished by 27Al 5QMAS NMR, whereas these sites are not differentiated by 27Al MAS and 3QMAS NMR. The isotropic chemical shift (δcs) and the quadrupolar product (PQ) were estimated to be 5.8 ppm and 2.6 MHz for Ala, 6.2 ppm and 3.0 MHz for Alb, and 6.7 ppm and 3.7 MHz for Alc, respectively. The three Al sites originated from geometric isomers with cis and trans structures, which have mutually different configurations of the OH groups around the central Al3+ ions. From the view point of symmetry for the OH groups, Ala and Alb in the upfield region were assigned to cis sites, and Alc in the downfield region was assigned to a trans site. The occurrence of multiple Al sites implies that Na-montmorillonite used in the present study has cis-vacant structure in the octahedral sheet. This is a reasonable insight, supported by the chemical composition and the differential thermal analysis data of the Na-montmorillonite.