A novel fluorene-bridged tetraketone monomer, 9,9-bis[(4-benzilyloxy)phenyl]fluorene (FLTK) was synthesized and characterized. The tetraketone was polymerized with various aromatic tetraamines to afford a series of polyphenylquinoxalines (PPQs). The obtained polymers were found to be soluble in common organic solvents such as N-methyl-2-pyrrolidone (NMP), chloroform and m-cresol. Flexible and tough PPQ films obtained by spin-casting their NMP solutions exhibited tensile strengths higher than 60 MPa. The films also demonstrated good thermal stability up to 500oC in nitrogen and glass transition temperatures higher than 280oC. In addition, the PPQ films exhibited good hydrolytic stability. High surface and volume resistivity retentions were achieved for the films after immersion or boiling in water for 24 h.