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Nitronium borates of NO2[B(OX)4] type with X = CF3CO and NO2 as ligands were synthesized, and their structures were determined by powder X-ray diffraction. Crystalline NO2[B(ONO2)4] is relatively stable at room temperature and undergoes transformation to B2O3 upon heating. The [B(CF3COO)4]− anion was obtained for the first time and characterized as a structural fragment of a solid compound. The possibility of reversible modification of the complex anion by replacement of the nitrate or trifluoroacetate ligand was demonstrated for the first time by the mutual transformations of NO2[B(ONO2)4] and NO2[B(CF3COO)4].