Dolomite is one of the most important resources for producing periclase (MgO) nanoparticles, which are of highly demanded in many industrial applications. For that reason, this study investigated to prepare MgO nanoparticles from dolomite through pyrohydrolysis–calcination processes. Each obtained product was characterized using X‐ray fluorescence, scanning electron microscope, X‐ray diffraction, and wet chemical and image processing analyses. Synthetic aragonite (CaCO3) crystals and CO2 gas were obtained as by‐products. The experimental results indicate that each obtained product was identified as a periclase mineral, and the production temperature played a curial role for producing pure MgO nanoparticles. However, the reactivity and particle size distribution of each product were strongly influenced by the production temperature. The particle size of the product obtained at various temperatures ranged from 180.05 nm to 6 μm depending on the production condition. We determined that the calcination process should be conducted to produce MgO nanoparticles. The proposed method brings a new perspective to researchers for the production of MgO nanoparticles from dolomite. © 2017 Curtin University and John Wiley & Sons, Ltd.