The invention discloses a (S)-1-(3-hydroxy-1-phenylpropyl)thiourea unilateral-modified Fe-Anderson-type heteropoly acid catalyst, a preparation method and an application thereof. According to the invention, ammonium molybdate and ferric sulfate are reacted under acidic condition to generate Fe-Anderson-type heteropoly acid parent; then heteropoly acid parent and tris(hydroxymethyl)aminomethane are reacted under backflow condition to obtain amino unilateral-modified Fe-Anderson-type polyoxometallate; (S)-1-(3-hydroxy-1-phenylpropyl)isorhodanate is synthesized; and finally, polyoxometallate and (S)-1-(3-hydroxy-1-phenylpropyl)isorhodanate are subjected to the reaction to obtain the target product. The preparation method has the advantages of simple process, high yield, mild reaction condition, and environment friendlessness; the catalyst can be used for a self-oxidation coupling reaction of a aryl methylamine compound, and has the advantages of environment pollution and high efficiency, high corresponding selectivity, and easy recovery and utilization.