The present invention relates to a process for preparing isocyanate homopolymers containing uretdione groups, in which the phosphinoboron compound of formula (I) are used as catalysts to catalyze the homopolymerization reaction of raw isocyanates, thereby obtaining a solution of isocyanate homopolymers having uretdione groups, then separating the solution and thus obtaining the isocyanate homopolymers containing uretdione groups. The isocyanate homopolymers containing uretdione groups prepared by this process have a high amount of the uretdione groups, wherein the dependence of the amount on the conversion rate of raw isocyanates is significantly ameliorated, with low chromaticities.