Aldosterone and renin measurement is a cornerstone for primary aldosteronism (PA) diagnosis, but different thresholds are used according to different assays. A fully automated chemiluminescence (CL) immunoassay for renin and aldosterone was recently proposed, showing good performance for PA screening by aldosterone to renin ratio (ARR). This study aimed to define the accuracy of this assay in the screening and in the most popular confirmatory test of autonomous aldosterone production, the intravenous saline loading test (ivSLT). We compared aldosterone results obtained by CL vs radioimmunoassay (RIA) in hypertensive patients investigated for PA (102 baseline and 85 after ivSLT). An excellent correlation was observed between RIA and CL in the entire population for aldosterone (r = 0.922) and ARR (r = 0.977). For ARR, Deming regression proved a good accordance between methods and, consistent with the fit model, our previous institutional ARR cut-off of 32 (pg ml-1)/(pg ml-1) corresponded to 20 pg ml-1 mU-1 l-1 in CL assay. However, the correlation was weaker in the low end of aldosterone concentrations (r = 0.676 for aldosterone < 100 pg ml-1), with a concordance of ivSLT results in only 68% of patients. CL assay displays a diagnostic performance very similar to RIA for ARR screening, but it is substantially inferior in the setting of confirmatory tests of autonomous aldosterone secretion, that is, ivSLT.