Reaction pathways and cation ordering mechanisms involved in the formation of the mineral dolomite in nature still remain poorly understood. This is mainly due to the experimental problems posed by the synthesis of dolomite at ambient conditions, which preclude monitoring its formation in reasonable time scales. However, processes leading to the crystallization of fully-ordered dolomite-like structures can be studied by conducting experiments with mineral analogues, which are more readily precipitated. In this paper we present a study of the formation of the dolomite-analogue norsethite [BaMg(CO3)2] from a slurry which was aged at room temperature during 14 days. We found that norsethite forms by two dissolution–crystallization reactions from an initial amorphous nano-sized precipitate. The first reaction produces a mineral assemblage composed by witherite [BaCO3], northupite [Na3Mg(CO3)2Cl] and norsethite. The second dissolution–crystallization process leads to the almost complete depletion of witherite and northupite in favor of norsethite. While the composition of norsethite crystals rapidly reaches a Ba/Mg = 1 ratio, X-ray diffraction peaks indicate an increase in the crystallinity of those crystals during the first 48 h of reaction. Simultaneously, Ba–Mg cation ordering increases, as shown by the evolution of intensity ratios of certain superstructure and structure reflections. Altogether, these results demonstrate that the formation of fully-ordered norsethite occurs by a sequence of solvent-mediated processes which involve a number of precursors. Our study also suggests that similar processes might lead to the formation of dolomite in natural environments.