The invention heterocyclic-sulfur fused naphthalenetetracarboxylic acid diimide derivatives, a preparation method and application thereof. In the preparation method, 2,3,6,7-tetrabromo-naphthalene diimide reacts with 2-alkyl cyanoacetate-ethylene-1,1-dithiol sodium salt, 2-mandelonitrile-ethylene-1,1-dithiol sodium salt or 2-(4-phenylacetonitrile bromide)-ethylene-1,1-dithiol sodium salt to prepare 1,3-heterocyclic-disulfide fused naphthalenetetracarboxylic acid diimide derivatives; and the 2,3,6,7-tetrabromo-naphthalene diimide reacts with 1,2-dicyanoethylene-1,2-dithiol sodium salt to prepare 1,4-dithiin cyclohexadiene-2,3-dinitrile fused naphthalenetetracarboxylic acid diimide derivatives, which further reacts to prepare alpha,beta-dicyanothiophene fused naphthalenetetracarboxylic acid diimide derivatives. The compounds are n-type organic semiconductor materials, and have wide application prospect in the field of organic electronics (organic field effect transistors, organic solar cells and the like).