Two-dimensional (2D) transition-metal borides (TMBs) are especially expected to exhibit excellent performance in various fields among electricity, superconductivity, magnetism, mechanics, biotechnology, battery, and catalysis. However, the synthesis of ultrathin TMB single crystals with ultrahigh phase purity was deemed extremely challenging and has not been realized till date. That is because TMBs have the most kinds of crystal structures among inorganic compounds, which possess generous phase structures with similar formation energies compared with other transition-metal compounds, attributing to the metalloid and electron-deficient characteristics of boron. Herein, for the first time, we demonstrate a chemical potential-modulated strategy to realize the precise synthesis of various ultrahigh-phase-purity (approximately 100%) ultrathin TMB single crystals, and the precision in the phase formation energy can reach as low as 0.01 eV per atom. The ultrathin MoB2 single crystals exhibit an ultrahigh Young's modulus of 517 GPa compared to other 2D materials. Our work establishes a chemical potential-modulated strategy to synthesize ultrathin single crystals with ultrahigh phase purity, especially those with similar formation energies, and undoubtedly provides excellent platforms for their extensive research and applications.