Direct arylation polymerization (DArP) is a synthetic method for conjugated polymers; in DArP, organometallic functionalization steps are omitted and there are no toxic byproducts. As a result, it is considered a more sustainable alternative compared to conventional methods such as Stille polymerization. To explore the possibility of DArP-based polymers as donor materials in organic solar cells (OSCs), a series of conjugated polymers based on the structure of PDCBT (poly[2,2''''-bis[[(2-butyloctyl)oxy]carbonyl][2,2':5',2'':5'',2'''-quaterthiophene]-5,5'''-diyl]) are synthesized using DArP and Stille polymerization. By controlling the monomer concentration and reaction time in DArP, DArP-5 with the highest M