<p>Organic ligand-protected metal nanoclusters locating at critical dimensions, represented by Au₁₃₀(SR)₅₀, hold irreplaceable information and application potential due to their unique structure and properties. However, their efficient synthesis is still challenging, especially for the ones protected by less hindered ligands. Herein, we report an induced synthetic approach toward the less hindered ligand-protected Au₁₃₀(SR)₅₀ nanoclusters. By incorporating 2-(diphenylphosphanyl)pyridine borane adduct (NPB) as an inducer, we successfully synthesized a series of Au₁₃₀(SR)₅₀ nanoclusters protected by thiols with less steric hindrance, including 1-propanthiol, 1-butanethiol, 1-pentanethiol, 1-hexanethiol, 1-heptanethiol, 1-octanethiol and 1-nonanethiol. This method features short reaction time, high yield, and straightforward purification. Further investigations revealed the ultrastability of less hindered ligand-protected Au₁₃₀(SR)₅₀ nanoclusters and the synergistic effect of nitrogen, phosphorus and boron sites on NPB for the induced synthesis.</p>