Background: Metabolic acidosis in patients with chronic kidney disease (CKD) is a common complication. A bicarbonate concentration in venous blood (V-HCO3−) is a key index for diagnosis and treatment initiation. The aim of our study is to evaluate usability of acid–base balance parameters of in blood taken simultaneously from peripheral artery and the vein. Methods: A total of 49 patients (median age 66 years [interquartile range IQR 45–75]), with CKD stage G4 or G5 were enrolled in this cross-sectional study. All patients were qualified for arteriovenous fistula creation in pre-dialysis period. The samples were taken during surgery, directly after dissection, and evaluated in a point of care testing analyzer. The arteriovenous difference in bicarbonate levels (Δ-HCO3−) was calculated. According to glomerular filtration rate (eGFR) the group was divided into Group A eGFR ≥ 10 mL/min/1.73 m2) and Group B eGFR 2). Results: In Group A Δ-HCO3− was significantly higher compared to Group B. No such differences were observed in the case of V-HCO3−. Δ-HCO3− positively correlated with eGFR. The discriminative power of Δ-HCO3− for predicting eGFR 2 was 0.72 (95% confidence interval [CI] = 0.551–0.88; p = 0.01) which provided 67% sensitivity and 75% specificity. The best cut-off was 0.5 mmol/L. Conclusions: The Δ-HCO3− lower than 0.5 mmol/L may be used as predictor of exhaust buffer capacity. The value of this tool should be tested in larger population.