The invention discloses a (R)-1-(1-(2-naphthyl) ethyl) thiourea modified Mn-Anderson type heteropoly acid catalyst, and a preparation method and an application thereof. The preparation method comprises the following steps: causing sodium molybdate react with tetrabutylammonium bromide to generate [N(C4H9)4]4[alpha-Mo8O26]; back-flowing [N(C4H9)4]4[alpha-Mo8O26] with trihydroxyamino methane and manganese acetate, thereby acquiring an organic bilateral amino-modified polyoxometallate; synthesizing (R)-1-(1-(2-naphthyl) ethyl) isothiocyanic acid by taking R-(+)-1-(2-naphthyl) ethylamine as a raw material; reacting with the organic bilateral amino-modified polyoxometallate, thereby acquiring a target catalyst. The preparation method provided by the invention is simple, is mild in reaction condition and is environmentally friendly; the acquired catalyst has the advantages of high efficiency, high corresponding selectivity and recyclability when the catalyst is applied to the olefin asymmetric double-hydroxylation reaction; the catalyst is fit for industrial production.