A series of modified poly(ether ether ketone)s containing different content of benzene pendant group in the molecular chain have been successfully synthesized with 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bisphenol A and 4,4′-difluorobenzophenone by nucleophilic substitution. The inherent viscosities of obtained polymers were in the range of 0.261–0.889 dLg−1. They were found to have high glass transition temperatures (Tg) of 150–168°C and 148–169°C (examined by DSC and DMA, respectively), good thermal stability with 5% weight-loss temperature (T5%) of 439–469°C. The tensile strengths of the obtained polymers were 67.7–86.6 MPa, and the storage modulus was over 0.9 GPa at about 140°C. The modified poly(ether ether ketone)s showed the excellent solubility property, they could be processed by solution method. Additionally, the obtained polymers had good optical transmittance (>70%) at 400 nm, suggesting that they have potential to be applied to the heat-resistant optical films.