The search for the alternatives to expensive synthesized conjugated polymers as interfaces in polymer solar cells (PSCs), which could largely decrease the cost and promote the commercialization process of PSCs, is now highly relevant. To introduce natural polymer as the interface layer for the high-efficiency PSCs would be a potential choice. In this study, a purely natural polysaccharide from ocean without any conjugated structure, sodium alginate (SA), is utilized as efficient electron transport layer (ETL) to replace the conjugated star molecule, poly [(9,9-bis(3-(N,NdiMethyl)-NethylaMMoiniuM-propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)]dibroMide (PFN-Br), and modify the aluminum (Al) electrode in conventional PSCs. The reduction of the work function of Al is successfully achieved by SA forming a dipole and keeping the ohmic contact at the interface. Meantime, the ideal charge transfer and exciton dissociation are realized, along with decreasing charge recombination, resulting in a comparable power conversion efficiency (PCE) with devices of PFN-Br as ETL. For poly([2,6-4,8-di(5-ethylhexylthienyebenzo[1,2-b; 3,3-b]dithiophene]3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl):[6,6]-phenyl-C-71-butyric acid methyl ester (PTB7-Th:PC71BM) system, PCE is increased to 9.5% and for Poly [(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2-b:4,5-b]dithio-phene))-alt-(5,5-(1,3-di-2-thienyl-5,7-bis(2-ethylhexyl)benzo[1,2-c:4,5-c]dithio-phene-4,8-dione)]:3,9-bis(2methylene-((3-(1,1-dicyanomethylene)-6,7-difluoro)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2,3-d]-s-inda-ceno[1,2-b:5,6-b] dithiophene (PM6:IT-4F) system, PCE 13.4%, respectively, which illustrates a promising future for photovoltaic research of natural alginate non-conjugated polyelectrolyte in conventional PSCs.