Rare earth borates are important due to their excellent properties, especially for optics. Here, we report the hydrothermal synthesis and structural determination by single-crystal X-ray diffraction of two new samarium polyborates with layered structures, being constituted by hexaborate chains. These hexaborate chains are connected by samarium polyhedra, forming dense sheets that further interact with each other by hydrogen bonding via isolated boric acid between these sheets. The third phase possesses a three-dimensional framework structure. The thermal stability of selective samples has been studied. The crystallization of samarium borate depends highly on the experimental conditions. Three samarium polyborates have been crystallized in very similar experimental conditions, clearly indicating that new lanthanide borate compounds with tailored structures may be prepared in the future by careful choice of physicochemical conditions.