The risk of B phytotoxicity due to high levels of B in irrigation water can be avoided by removing B from the water, before its use, through adsorption on certain adsorbents, such as magnesia (industrial MgO), if the latter can be proven to be an effective and easy to handle means for B removal. In addition, if such a material is applied as a fertilizer after its use and the adsorbed B is easily released into the soil solution, B phytotoxicity could constitute a potential hazard. The objectives of this work were to: (a) establish the optimum working conditions (equilibration time, solution to adsorbent ratio, and particle size of the adsorbent) for B adsorption, (b) assess the magnitude of B adsorption by magnesia, both in capacity and intensity terms, as well as the influence of temperature, (c) study B desorbability from magnesia, spiked with B at two rates, 5 and 0.5 mg g−1, and (d) compare the results from b and c to those obtained using reagent grade MgO. The results showed that the time to achieve equilibrium depended on the B concentration of the external solution and ranged from 6 h (for B ≤ 10 mg L−1) to 48 h (for B ≥ 50 mg L−1). The percentage of B adsorbed decreased as the volume of external solution to adsorbent increased and a working ratio of 50:1 was selected. For magnesia, B adsorption was particle size dependent with the smallest fraction (<0.1 mm) sorbing more B than the other three fractions studied (0.1–1.0, 1.1–2.0, 2.1–4.0 mm). Boron adsorption was conducted under strongly alkaline pH (10.3 ± 0.2 and 10.4 ± 0.1 for the reagent and magnesia, respectively) and increased with temperature. Both adsorbents exhibited a high B adsorption capacity (Langmuir maximum values were 5.85 ± 0.39 and 4.45 ± 1.31 mg B g−1 for the reagent and magnesia, respectively) comparable to other metal oxides. However, the reagent grade MgO seemed to be superior to magnesia in terms of capacity and strength of B retention. This superiority of the reagent was attributed to its greater surface area (34.7 compared with 5.8 m2 g−1 for magnesia) and to its conversion to Mg(OH)2 during the adsorption process, whereas magnesia remained unaltered, as was evident from X-ray diffractograms. Based on this data, magnesia seems to be an effective means for removing excess B from irrigation water, particularly if a material of fine particle size is used. Boron desorbability after 240 h of desorption time was more pronounced for magnesia reaching up to 55 and 60% of the amount of B added, at the spiked rates of 5 and 0.5 mg g−1, respectively. Although these figures indicate that approximately half of the amount of B added remained adsorbed, they cannot be easily extrapolated to field conditions, and if B-laden magnesia is applied to soils, the possibility of B phytotoxicity cannot be excluded.