Background/Objectives: Elevated RDW has emerged in cardiac surgery as a potential means of preoperative risk stratification with the capacity to predict short- and long-term postoperative mortality, acute kidney injury, and postoperative atrial fibrillation. The question as to whether perioperative hemodynamic instability may be predicted by such a marker remains a topic of ongoing debate. The aim of this study was to explore the relationship between preoperative RDW and prolonged postoperative catecholamine use in minimally invasive mitral valve surgery. Methods: We performed a retrospective monocentric cohort study in an academic hospital; we enrolled patients who had undergone minimally invasive mitral valve surgery (including both robot-assisted and non-robot-assisted procedures) between January 2019 and December 2022. We considered the use of inotropes and/or vasopressors for at least twelve hours after post-surgery ICU admission to qualify as the prolonged postoperative use of catecholamines (PPUC). The RDW was obtained from the routine full blood count analysis performed upon admission or a maximum of 72 h before surgery. We also performed a multivariable logistic regression analysis with PPUC as the dependent variable. Results: We finally enrolled 343 patients. Upon multivariate analysis, RDW >14.4% was independently associated with prolonged postoperative catecholamine use when compared to the reference group (OR 2.62 [1.06-4.84]; p = 0.03). Moreover, the EuroSCORE II score (OR 1.38 [1.03-1.85]; p = 0.03), the cross-clamp time (OR 1.01 [1.01-1.02]; p < 0.01), and robot-assisted mitral valve surgery (OR 0.53 [0.30-0.93]; p < 0.03) were independently associated with the prolonged postoperative use of catecholamines. Conclusions: This study identified that an elevated preoperative RDW (>14.4%), the EuroSCORE II score, and the cross-clamp time independently predict prolonged postoperative catecholamine use in minimally invasive mitral valve surgery patients. Conversely, the robot-assisted approach was associated with a smaller hemodynamic impairment.