The invention discloses perylene tetracarboxylic carboxylic ester group polymer acceptor materials and application thereof to a solar battery. The materials include a structure as refined in formula 1, in the formula 1, M is diazosulfide, dithienyl diazosulfide, selenole, dithienyl selenole, diselenium thiophene selenole, thiophene, dithiophene, terthienyl, benzene, selenophen, diselenide thiophene, terselenide thiophene, thiophene thiophthene, benzo dithiophene, benzo ditellurium thiophene, benzo ditellurium thiophene, or one of derivatives made on the basis of the compounds. R is a linear chain with more than four carbon atoms, a branched chain or an alkyl chain containing different heteroatoms. N is a natural number of 1-1000. By introducing comonomer M on the perylene ring skeletons 1, 7 positions, the level structure of polymer materials can be adjusted, and at the same time, optical property is improved, and use ratio of the materials to light is enhanced. By introducing R, dissolubility of the polymer materials can be adjusted, and utilization of a solution processing technology with low cost is facilitated. The materials can be applied to the field of organic optoelectronics.