The determination of manganese in the presence of iron and chromium by differential pulse voltammetry and fundamental harmonic alternating current voltammetry was compared, including the case of very high element concentration ratios. The voltammetric measurements were carried out using a stationary mercury electrode in ammonia-ammonium chloride buffer (pH 9.6). The analytical procedure was verified by the analysis of the standard reference materials Portland Cement BCS 372, Spectrographic Zinc Spelter NBS-SRM 631, Stainless Steel (AISI 321) NBS-SRM 121d and Highly Alloyed Steel Eurostandard 281-1. Precision and accuracy, expressed as relative standard deviation and relative error respectively, were of the order of 3–5%, while the detection limit for each element was around 1 × 10 −9 M. The standard addition technique improved the resolution of the voltammetric methods, within a maximum experimental error of 5%, even in the case of very high concentration ratios, that is outside the non-interference concentration ratios 69:1 > c Fe: c Mn > 1:74; 35:1 > c Fe: c Cr > 1:30 and 63:1 > c Fe: c Mn > 1:65; 32:1 > c Fe: c Cr > 1:31 for the differential pulse and alternating current techniques respectively, extrapolating the linear section of the i p vs. concentration analytical calibration function for the element present at the lowest concentration. In contrast, the element with the greatest concentration was determined by the relevant calibration curve.