This paper attempts to describe a plausible scheme of reaction(s) that governs the electrodeposition of boron from melts containing KCl, KF and KBF4 (at 1073 K). Four different stoichiometric equations were formulated based on the existence of various chloride-fluoride complexes derived from the fluoroborate anion. During the electrolysis all these chloride-fluoride complex anions of boron would undergo decomposition. The net variation in the ratio n(Cl-)/n(F-) thus computed based on these four equations by assuming uniform depletion of boron from the melt due to electrodeposition was compared with the experimental values obtained during many electrowinning runs. These analyses describe the progress of the electrodeposition of boron from KCl, KF and KBF4 melt. (C) 2011 Elsevier Ltd. All rights reserved.