The electrothermal process of magnesium metal production is a promising route, where large sized internally heated reactor is used for magnesium production resulting in less energy and labour intensive and high space-time yield process. However, the dissolution behavior of dolime in the electrothermal slag has been found critical for the process optimization. In this paper, the dissolution kinetics of the dolime in the slag was discussed. Quaternary slag (CaO-Al2O3-SiO2-MgO) was prepared having basicity CaO/SiO2 ≥ 1.8 and Al2O3/SiO2 ≥ 0.26 for dolime dissolution studies by static hot dip method. Prior to the experiments, FactSage calculations were carried out varying temperatures and slag compositions. In the kinetic studies, dolime particles 10–15 mm size was added in slag melted at 1450, 1500 and 1550°C and samples were taken at various time intervals. The chemical analysis of slag sample was carried out to investigate the dissolution kinetics to establish the rate expression. The activation energy for the process was calculated for different models used in study and was found to be in the range of 130–270 kJ/mol. SEM analysis was done for surface analysis of reacted particles. This study would be helpful in optimizing the dolime charging rate during pilot scale trials for electrothermal magnesium production at CSIR-NML, Jamshedpur.