The modified single-walled carbon nanotubes (m-SWCNTs)/poly(ether ether ketone) (PEEK) composites were prepared by solution blending and melt blending, respectively. The mechanical, dielectric, and frictional performances of the m-SWCNTs/PEEK composites obtained by different processing technic were investigated. The poly(aryl ether ketone)s with pyrene (PAEK-Pys) were synthesized through iridium-catalyzed C−H borylation followed by Suzuki coupling. PAEK-Pys were characterized using ultraviolet–visible spectroscopy, proton nuclear magnetic resonance spectroscopy, and gel permeation chromatography. The polymers were then used for surface modification of pristine SWCNTs. Finally, the m-SWCNTs were used to prepare m-SWCNTs/PEEK composites via co-blending in solution or melt. The mechanical, frictional, and dielectric performance of the m-SWCNTs/PEEK composite by solution blending were better than these in m-SWCNTs/PEEK composite by melt blending. These results suggest that the method of solution blending is more favorable for the dispersion of the SWCNTs in PEEK.