A comparative kinetic Monte Carlo (kMC) modeling study is presented for the synthesis of poly(2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylenevinylene) (MDMO‐PPV) via the sulfinyl and dithiocarbamate (DTC) precursor route. The sulfinyl precursor route allows a much faster polymerization toward highly regioregular and high molar mass MDMO‐PPV starting from non‐equimolar amounts of the isomeric sulfinyl premonomers. In the DTC precursor route, the polymerization can be started from a single dithiocarbamate premonomer and a higher yield can be reached. In contrast, synthesis of highly regioregular MDMO‐PPV via the sulfinyl precursor route requires separation of the isomeric premonomers after their synthesis and before polymerization.