The synthesis of hydrophilic conjugated polymers typically relies on organometallic coupling methodologies. Here we present an approach to prepare polar poly(arylene vinylene)s (PAVs) in water using the Horner-Wadsworth-Emmons (HWE) reaction. The additional preparation of discrete arylene vinylene (AVs) afforded insight into HWE kinetics and regioselectivity. Nine novel PAVs and AVs were synthesized, characterized by UV-vis absorption and ultraviolet photoelectron spectroscopy, and studied for their utility in sensing and photovoltaic applications.