Abstract: In this work, continuous carbon fiber (CCF)/polyetheretherketone (PEEK) composites were prepared by using polyethersulfone (PES) as tertiary component and activated PES as surface modifier for CCF respectively. The research focuses on the effects of the preparation process on the properties of the CCF/PEEK composites. The results show that for the CCF/PEEK composites prepared with PES as tertiary component, when 16wt% of CCF is filled, the surface resistance decreases to 10⁷-10⁹ Ω, appearing conductive percolation state, and the friction coefficient reduces to the lowest value of 0.2430. The tensile strength, bending strength and impact strength of CCF/PEEK composites filled with 30wt% of CCF with surface modifier by activated PES are increased to 236.2 MPa, 345.1 MPa and 12.3 kJ/m² respectively, which are increased by 13.69%, 21.70% and 36.97% respectively, compared with the CCF30/PEEK composites without PES modification, with the good dispersion of CCF and better interface adhesion between PEEK and CCF surface modified by PES. The tribological results indicate that the friction properties of the composites depend not only on the distribution of CCF in the matrix, but also on the interface force between CCF and the matrix.