Conjugated polymers have unique electrical and optical properties and have been used in devices such as organic solar cell and organic field effect transistor. The molecular weight of the conjugated polymer is an important factor in determining device performance. The high reproducibility of the flow synthesis system enabled accurate investigation of the relationship between reaction conditions and molecular weight in Stille polycondensation of conjugated polymers. Here, a conjugated polymer, PTB7, was synthesized in a customized flow reactor under various catalyst and solvent combinations, and their effect on molecular weight was studied. Specifically, common palladium catalysts (Pd(PPh₃)₄ and Pd₂(dba)₃) were screened in three different solvents (toluene, chlorobenzene, and o-xylene). A significant difference in molecular weight was observed depending on the type of solvent when using Pd₂(dba)₃ as a catalyst. It was discovered that the solubility of both the catalyst and PTB7 in the solvent played a critical role in determining the molecular weight of the polymer. By using the Pd₂(dba)₃ catalyst system, a high number-averaged molecular weight (Mn) for the PTB7, ranging from 41.7 to 51.5 kDa, was achieved. This was 16 times higher than that obtained with the Pd(PPh₃)₄ catalyst system in any solvent. However, the Pd(PPh₃)₄ catalyst system showed a high compatibility with dimethylformamide (DMF) co-solvent, and the Mn of PTB7 synthesized with Pd(PPh₃)₄ catalyst showed a significant increase, ranging from 53.9 to 58.7 kDa, while the Mn of PTB7 synthesized with Pd₂(dba)₃ catalyst decreased to 10.9 to 15.0 kDa. The results can provide valuable guidance for optimizing reaction conditions in the future synthesis of conjugated polymers in a flow reactor to achieve the desired molecular weight.