The invention relates to a novel organic bismuth complex, a preparation method and catalytic application thereof. The method is characterized in that: a common organic solvent is adopted as the reaction solvent, diphenylbismuth chloride containing a bridge type nitrogen atom ligand and cheap and easily available arylboronic acid are adopted as the raw materials, nickel acetate is employed to catalyze reaction, and the novel organic bismuth (III) complex catalyst (I) with high yield and high selectivity can be obtained. The catalyst has good stability, is recoverable, and shows excellent catalytic activity in catalyzing the hydroamination reaction of aryl alkyne and an aniline derivative. The method has the advantages of low cost, high yield, simple operation, no pollution, etc., and has feasibility in realization of industrial production.