Delirium is a common neurological complication in patients with advanced heart failure (ADHF) following left ventricular assist device (LVAD) implantation, significantly impacting recovery. This study aimed to analyze non-contrast computed tomography (CT) scans of the brain in ADHF patients undergoing LVAD implantation to determine the association between pre-existing brain atrophy and postoperative delirium. A study involving 166 ADHF patients was conducted from March 2020 to July 2023. Non-contrast CT scans were analyzed using advanced quantitative neuroimaging techniques before implantation. The primary marker assessed was the lateral ventricle fraction (LVF), with secondary markers including cortical gray matter fraction (cGMF), white matter fraction (WMF), basal ganglia fraction (BGF), and thalamus fraction (TLF). A total of 56 patients (33%) experienced postoperative delirium within two weeks of implantation. Patients with delirium were older and exhibited greater brain atrophy, indicated by higher LVF and lower cGMF, WMF, BGF, and TLF values. The occurrence of delirium was strongly associated with age, and ventricular enlargement, primarily in the lateral ventricles. LVF effectively predicted delirium development, regardless of age. Preoperative brain volumetric analysis, particularly of the lateral ventricles, may be crucial in identifying patients at risk for postoperative delirium, enhancing postoperative management, and improving outcomes for LVAD recipients.