Fluoropolymers have useful properties including high thermal stability, chemical resistance, low dielectric constants, and both hydrophobic and oleophobic character, as compared to non-fluorinated analogues. Meanwhile, Diels-Alder polyphenylenes (DAPPs) are known for thermal stability as well as their rigid structure and glassy physical characteristics, which have led to a variety of film and membrane applications. This dissertation merges these two fields by demonstrating a novel and general synthetic approach to highly fluorinated DAPPs. These polymers are expected to retain the physical characteristics of glassy, non-fluorinated DAPPs while also incorporating the desirable attributes of fluoropolymers. The polymer synthesis described herein is based on the well-established polycondensation of bis(cyclopentadienone) (CPD) monomers and dialkynes. Our first main scientific contribution is a general method for preparing CPDs containing both a fluoroaromatic linker and variable fluoroaromatic head-groups. Our CPD synthesis uses nucleophilic aromatic substitution reactions of cyclopentadienyl anions and perfluoroarenes, as well as a new catalytic method of converting cyclopentadiene methylene (CH₂) groups into the corresponding ketones (C=O) that is the primary dissertation subject of Brian S. Hickory in our laboratory. The overall synthesis is notable for its use of inexpensive starting materials, its efficiency, and its structural versatility. Our second main contribution is the synthesis of novel highly fluorinated Diels-Alder polyphenylenes (DAPPs). Fluorinated DAPPs varied in their molecular weight, in the identity of the lateral fluoroaryl substituent (pentafluoro-phenyl or tetrafluoro-4-pyridyl), and in the structure of the aromatic dialkyne monomer. These polymers are glassy materials with high glass transition temperatures and high thermal stability. Since the polyphenylene structure is intrinsically rigid, the polymers form brittle films even at molecular weights of over 30,000 (M_w). Unlike many fluoropolymers, the fluorinated DAPPs are freely soluble in common organic solvents such as tetrahydrofuran and chloroform. An unknown side reaction competes with the polymer propagation and reduces the highest obtainable molecular weights, which limit the ability to form films. However, a stoichiometric imbalance leads to highly fluorinated polyphenylene oligomers terminated with either alkyne or CPD end groups (M_n = 9000). Because preliminary experiments had shown that the desired Diels-Alder propagation reaction was slower than expected, we also undertook a detailed model study of the reaction conditions needed for Diels-Alder reactions of fluorinated CPDs and aromatic alkynes. These experiments showed that protic polar solvents (e.g., m-cresol) and conventional heating at ca. 150 °C optimize reaction rate while minimizing side-reactions that can contribute to lower molecular weight in corresponding polymerization reactions. / Ph. D.