This paper describes a simple new strategy for preparing poly( 9,9-dialkylfluorenyl-2,7-vinylenes) (PFVs) having high molecular weights and no detectable saturated defects along the conjugated backbone. The new route utilizes a modified Horner-Emmons method by coupling suitably designed comonomers to form the targeted conjugated polymers. The newly prepared PFVs were directly compared to PFVs prepared via a previously established Gilch polymerization route. The structure and optical properties of all PFVs were characterized by gel permeation chromatography (GPC), NMR spectroscopy, UV-vis, fluorescence, and photoluminescence spectroscopy. The findings indicate that the modified Horner-Emmons route gave PFVs with lower molecular weights but substantially higher yields and fewer defects than those prepared by using the Gilch route.