ABSTRACT The dielectric constant, thermal stability, and mechanical properties of dielectric materials play a crucial role in advancing electronic devices toward high performance and integration density. However, the comprehensive properties of existing PEEK‐based low dielectric materials are insufficient to meet future demands. In this work, hollow molybdenum disulfide nanospheres (hMoS 2 ) were prepared by the template method and hydrothermal reaction, and then modified with 1H,1H,2H,2H‐Perfluorodecanethiol (PFDT) to obtain fluorinated hollow molybdenum disulfide nanospheres (F‐hMoS 2 ). Subsequently, the F‐hMoS 2 was blended with poly (ether ether ketone) (PEEK) to form F‐hMoS 2 /PEEK composites. Morphological, structural, and chemical composition characterization confirmed the successful synthesis of F‐hMoS 2 . The results showed that the addition of F‐hMoS 2 effectively reduced the dielectric constant of PEEK composites while enhancing their thermal stability and mechanical properties. The F‐hMoS 2 /PEEK‐0.6 composite exhibited a dielectric constant of 2.75 at 1 MHz, a thermal decomposition temperature of 541.7°C, and a tensile strength of 101.7 MPa. In addition, the composite exhibited better frequency stability, a higher glass transition temperature (154.5°C), and storage modulus (3200 MPa) compared with pure PEEK. This work establishes a materials design paradigm for the practical application of PEEK in electronic devices.