The occurrence of heavy metal ions in water is intractable, and it has currently become a serious environmental issue to deal with. The effects of calcining magnesium oxide at 650 °C and the impacts on the adsorption of pentavalent arsenic from water are reported in this paper. The pore nature of a material has a direct impact on its ability to function as an adsorbent for its respective pollutant. Calcining magnesium oxide is not only beneficial in enhancing its purity but has also been proven to increase the pore size distribution. Magnesium oxide, as an exceptionally important inorganic material, has been widely studied in view of its unique surface properties, but the correlation between its surface structure and physicochemical performance is still scarce. In this paper, magnesium oxide nanoparticles calcined at 650 °C are assessed to remove the negatively charged arsenate ions from an aqueous solution. The increased pore size distribution was able to give an experimental maximum adsorption capacity of 115.27 mg/g with an adsorbent dosage of 0.5 g/L. Non-linear kinetics and isotherm models were studied to identify the adsorption process of ions onto the calcined nanoparticles. From the adsorption kinetics study, the non-linear pseudo-first order showed an effective adsorption mechanism, and the most suitable adsorption isotherm was the non-linear Freundlich isotherm. The resultingR2values of other kinetic models, namely Webber-Morris and Elovich, were still below those of the non-linear pseudo-first-order model. The regeneration of magnesium oxide in the adsorption of negatively charged ions was determined by making comparisons between fresh and recycled adsorbent that has been treated with a 1 M NaOH solution.