Objectives This study aims to evaluate the concordance between blood gas and biochemical measurement methods for sodium and potassium levels in elderly and non-elderly patients within an emergency department (ED) setting. Methods A retrospective method comparison study was conducted at an ED from February 1, 2023, to March 1, 2023. The study included 414 patients, categorized into "elderly" (aged 65 and above; n = 138, 33.3%) and "non-elderly" (aged 18 to 64; n = 276, 66.7%) groups. Concordance was assessed using Bland-Altman, Passing-Bablok, and Lin's concordance correlation methods. Results In sodium measurements, the elderly group exhibited an average bias of -1.52 mEq/L (95% confidence interval [CI] -2.12 to -0.92), with lower and upper limits of agreement (LoA) at -8.46 and 5.42 mEq/L, respectively, indicating a broader variance than non-elderly patients, who showed an average bias of -0.82 mEq/L with limits of -4.97 to 3.32 mEq/L. For potassium, the elderly group's average bias was -0.46 mEq/L (95% CI -0.36 to -0.57), with limits of agreement from -1.68 to 0.75 mEq/L, compared to non-elderly patients with a bias of -0.29 mEq/L and limits of -0.71 to 0.13 mEq/L. Furthermore, concordance correlation coefficients revealed a reduced agreement in the elderly for both sodium (r ccc = 0.799) and potassium (r ccc = 0.529) compared to the non-elderly cohort (sodium r ccc = 0.821, potassium r ccc = 0.715). Conclusion The study identifies significant discrepancies in sodium and potassium levels between elderly and non-elderly patients, suggesting a need for diagnostic precision. It emphasizes the importance of customizing diagnostic approaches to better serve the elderly population in EDs.