Alzheimer's disease (AD) presents typically gray matter atrophy and white matter abnormalities in neuroimaging, suggesting that the gray-white matter boundary could be altered in individuals with AD. The purpose of this study was to explore differences of gray-white matter boundary Z-score (gwBZ) and its tissue volume (gwBTV) between patients with AD, amnestic mild cognitive impairment (MCI), and cognitively normal (CN) elderly participants. Three-dimensional T1-weight images of a total of 227 participants were prospectively obtained from our institute from 2006 to 2022 to map gwBZ and gwBTV on images. Statistical analyses of gwBZ and gwBTV were performed to compare the three groups (AD, MCI, CN), to assess their correlations with age and Korean version of the Mini-Mental State Examination (K-MMSE), and to evaluate their effects on AD classification in the hippocampus. This study included 62 CN participants (71.8 ± 4.8 years, 20 males, 42 females), 72 MCI participants (72.6 ± 5.1 years, 23 males, 49 females), and 93 AD participants (73.6 ± 7.7 years, 22 males, 71 females). The AD group had lower gwBZ and gwBTV than CN and MCI groups. K-MMSE showed positive correlations with gwBZ and gwBTV whereas age showed negative correlations with gwBZ and gwBTV. The combination of gwBZ or gwBTV with K-MMSE had a high accuracy in classifying AD from CN in the hippocampus with an area under curve (AUC) value of 0.972 for both. gwBZ and gwBTV were reduced in AD. They were correlated with cognitive function and age. Moreover, gwBZ or gwBTV combined with K-MMSE had a high accuracy in differentiating AD from CN in the hippocampus. These findings suggest that evaluating gwBZ and gwBTV in AD brain could be a useful tool for monitoring AD progression and diagnosis.