Conjugated polymers have attracted much scientific and technological research interest during the past few decades because of their potential use as semiconductors and electroactive materials in diverse applications. Among the conjugated polymers, significant attention has been paid to polyfluorene (PF) and PF derivatives, especially for polymer light-emitting diodes (PLEDs) applications, because of their high photoluminescence (PL) quantum efficiency, thermal stability, and facile color tunability. Recently, research interest in PFs has been extended to organic thin-film transistors (OTFTs), organic photovoltaic devices (OPVs), and other electronic devices. Oxidative, Suzuki, and Yamamoto coupling reactions using various catalysts have enabled the synthesis of tailored PFs for use in many organic electronics applications. This chapter focuses on the diverse synthetic methods for PFs, including the experimental details, and also discusses their applications.