Cerebral and microvascular perfusion is reduced in atrial fibrillation (AF). Maintenance of brain perfusion is important in acute disease and long-term course. Assessment of brain perfusion and oxygenation is difficult in clinical practice. Our study aimed to determine changes in cerebral tissue oxygen saturation (SctO2) with bedside near-infrared spectroscopy (NIRS). Twenty patients (mean age 67.7 ± 10.2 years, 50% men) in whom electrical cardioversion (CV) was successful were prospectively studied. Ten patients (mean age 64.2 ± 7.7 years, 80% men) in whom CV was not successful served as control group. Bilateral SctO2, mean arterial pressure (MAP), arterial oxygen saturation (SaO2), and heart rate were recorded and changes of all parameters before and after CV were compared between the groups. Our results show an increase in SctO2 after successful CV that was significantly higher compared with patients who remained in AF (right SctO2 3.25 ± 2.5 vs. -0.13 ± 0.52%, P = 0.001; left SctO2 4.27 ± 3.56 vs. -0.38 ± 2.4%, P < 0.001). Neither arterial blood pressure nor SaO2 changes differed significantly between the two groups. No correlation could be detected between the significant increase of SctO2 after successful CV and arterial blood pressure, SaO2, or heart rate. Cerebral tissue oxygen saturation increases significantly after restoration of sinus rhythm. Near-infrared spectroscopy monitoring can identify changes of SctO2 after successful CV of AF independent from standard monitoring parameters (MAP, SaO2). Near-infrared spectroscopy can be used to detect cerebral oxygen saturation deficits in AF patients or patients at high risk for AF. Clinical applications may include monitoring during ablation procedures and in critical care.