Researchers have observed that executive functioning ability declines before memory among individuals with presymptomatic Alzheimer's pathology. Whether this change in cognitive ability is associated with earlier neuroanatomical structural change is explored in the current study. Specifically, the purpose of the current study was to investigate earlier neuroanatomical volume changes in the hippocampus, precuneus, orbitofrontal cortex, and gray matter among individuals with presymptomatic Alzheimer's pathology. Participants included 21 cognitively healthy older adults with normal levels of cerebrospinal fluid (CSF) beta-amyloid and tau (CH-NAT) and 18 cognitively healthy individuals with pathological levels of CSF beta-amyloid and tau (CH-PAT), designated as the presymptomatic Alzheimer's pathology group. Study findings suggest that individuals in the CH-PAT group had overall smaller volume levels among all neuroanatomical structures analyzed than those in the CH-NAT group, particularly in the right lateral orbitofrontal cortex. Members of the CH-PAT group also displayed poorer executive functioning ability. However, poorer executive functioning ability was associated with smaller left hippocampal volume among females, but not males, in the CH-NAT group.