The structure, IR absorption and luminescence spectra of solid solutions of Lu 0.99 -x Gd x Eu 0.01 BO 3 at 0 ≤ x ≤ 0.15 were studied. The correspondence between the structure and spectral characteristics of these compounds was established. It is shown that at x ≤ 0.05, the orthoborates Lu 0.99 -x Gd x Eu 0.01 BO 3 , consisting of lutetium borate LuBO 3 , which has two stable structural modifications (calcite and vaterite), and gadolinium borate GdBO 3 , which has only one structural modification (vaterite), form a solid solution with a calcite structure and a microcrystal size of 15-20 μm. As x increases, the amount of vaterite phase increases sequentially, and at x ≥ 0.1, the entire volume of the sample has a vaterite structure. At Gd 3+ concentration in the range of 0.05 < x ≤ 0.1, the samples of Lu 0.99 -x Gd x Eu 0.01 BO 3 are two-phase. It is shown for the first time that at x > 0.05, the vaterite phase appears both in the volume of large microcrystals (15-20 μm) and in the form of small microcrystals (1-2 μm).