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This work reports the effects of potassium bromide (KBr) on the electrodeposition of manganese on copper from a DES consisting of a stoichiometric 1:2 mix of choline chloride and ethylene glycol (Ethaline 200). The speciation of MnCl2.4H2O in Ethaline 200 has been investigated using UV–vis spectroscopy, in particular with regard to the addition of KBr to the plating bath, for which no apparent change in the Mn species was noted. This said, the physical properties of the manganese deposits themselves were found to have been considerably improved in comparison to when KBr was omitted from the bath; indeed, the actual adhesion of Mn was achieved for the first time on a copper substrate, somewhat remarkably producing a coating of some considerable thickness. Given its clear electrochemical behavior of the Mn liquid were subsequently determined via cyclic voltammetry method. A reduction in the peak current of Mn was noted on addition of KBr. The mechanism of Mn deposition has been examined via chronocoulometry and chronoamperometry. Surface analyses of Mn deposits have been conducted via SEM/EDX, AFM, and XRD, from which improvements to the Mn surface coatings in depositions performed from an electrolyte containing 0.1 M KBr were noted. [ABSTRACT FROM AUTHOR]