The growing need for high-power and compact-size microelectronic integrated circuits (ICs) in modern microelectronic industries and 5G communication systems demands low dielectric constant (κ) polymer dielectrics with excellent temperature capability, mechanical property and processability. However, conventional molecular design strategies often face difficulties of a trade-off between optimizing the dielectric performance of polymers and maintaining the aforementioned properties. Herein, we present an innovative and facile strategy that utilizes the space charge distribution characteristics of the target co-monomer to solve this trade-off. Based on this design strategy, a novel polyaryl ether ketone (PAEK) with two different charge distribution units (BAF and SBI) was designed and synthesized. Both the experimental results and computational simulations confirm that these two components serve to weaken the polarization of molecular chains in the electric field, induce higher molecular chain packing density and fewer weaknesses, and synchronously regulate the κ, dielectric loss (tan δ), thermal and mechanical properties and processability by generating a strong inter-chain electrostatic interaction. The resultant copolymer, PAEK-4F6S, exhibits exceptional low κ and tan δ values of 1.98 and 0.0024 at 1 MHz, respectively, and these values remain stable over a broad frequency (1–10⁶ Hz, 8.2–12.4 GHz) and temperature range (30–150 °C). Furthermore, the resultant copolymer demonstrates excellent thermal stability and mechanical properties, with a glass transition temperature (T_g) of 195 °C, 5 wt% decomposition temperature (T_d5%) of 498 °C under N₂, tensile strength of 63.5 MPa and tensile modulus of 1011.2 MPa, respectively. The synthesis procedure of these resultant copolymers is facile, and they are found to have favorable solution and melt processing properties, making them suitable for processing and scalable production. More importantly, this design strategy is beneficial for lowering the κ and tan δ values, and simultaneously enhancing the comprehensive performances of the objective polymers, which provides a completely novel and facile approach for the design and fabrication of high performance low-κ polymers suitable for the needs of microelectronics and communication fields.