Sodium alginate (SA), as a natural marine biopolymer, possesses many merits such as super-easy accessibility from the ocean, low cost, nontoxicity, and no synthesis for practical application. For the chemical structure, SA has enough lone electron pairs of oxygen atoms in the backbone and short branched chains, which is expected to passivate oxygen vacancy on the surface of the ZnO cathode buffer layer to improve the photovoltaic performance. Herein, it was applied to modify the surface trap of the ZnO layer in fullerene and non-fullerene polymer solar cells (PSCs). The defects were successfully reduced, and the trap-assisted recombination decreased. In a PTB7-Th:PC71BM system, power conversion efficiency (PCE) was improved from 8.06% to 9.36%. In the PM6:IT-4F system, PCE was enhanced from 12.13% to 13.08%. The addition of SA did not destroy the stability of the device. Overall, this work demonstrates the potential for preparing devices with long-time stability and industrial manufacture of PSCs by using biological materials in the future.