Conjugated polymers have received widespread interest as optoelectronic materials. Recently, these macromolecules have been adopted for biologically relevant applications, such as sensors, imaging agents, and drug delivery vectors. A major limitation of the chemistry used to prepare these classes of compounds is that the resultant polymers themselves are not tolerant to water or are not inherently water-soluble. For example, the most controlled method of conjugated polymer synthesis, the Kumada catalyst transfer polymerization (KCTP), requires stringent drying of monomers, catalysts, and other reagents. Here, we describe an approach to use a water-scavenging Grignard reagent to alleviate many of the shortcomings that currently hinder the synthesis of water-soluble conjugated polymers. This method shows improved polymerization performance in both traditional conjugated polymer synthesis as well as more challenging syntheses of polar hygroscopic polymers that are of interest for biological applications.