(1) Objective: To reveal the correlation between the hemoglobin-to-red cell distribution width ratio (HRR) and all-cause mortality (ACM) among the septic patients with atrial fibrillation. (2) Methods: Specific clinical information was collected from the Medical Information Mart for Intensive IV (MIMIC-IV) database. The optimal cut-off value of HRR was calculated through ROC curve analysis conducted by using the maximum Youden index for the prediction of survival status. In addition, univariable and multivariable Cox regressive analyses were carried out to assess the prognostic significance of HRR and the Kaplan-Meier (K-M) analysis was conducted to draw the survival curves. Then, the 1:1 propensity score matching (PSM) method was adopted to improve the reliability of research result while balancing the unintended influence of underlying confounders. (3) Results: There were 9228 patients participating in this retrospective cohort study. The optimal cut-off value of the HRR was determined as 5.877 for in-hospital mortality. The PSM was performed to identify 2931 pairs of score-matched patients, with balanced differences exhibited by nearly all variables. According to the K-M analysis, those patients with a lower HRR than 5.877 showed a significantly higher level of in-hospital mortality, 28-day mortality, and 90-day mortality, compared to the patients with HRR >= 5.877 (p < 0.001). After the adjustment of possible confounders, those patients whose HRR was below 5.877 had a significantly higher level of in-hospital mortality than the patients with HRR >= 5.877, as revealed by the multivariable Cox regression analysis (HR = 1.142, 95%CI: 1.210-1.648, p < 0.001). Similarly, the ACM remained substantially higher in those patients with a lower HRR than in the patients with higher HRR after PSM. (4) Conclusion: A lower HRR (<5.877) was evidently associated with an increased risk of ACM, which made it applicable as a prognostic predictor of clinical outcomes for those septic patients with atrial fibrillation.