Cylindrical vector beams (CVBs), with non-uniform state of polarizations, have become an indispensable tool in many areas of science and technology. However, little research has explored high power CVBs at the femtosecond regime. In this paper, we report on the generation of high quality CVBs with high peak power and femtosecond pulse duration in a fiber chirpedpulse amplification laser system. The radially (azimuthally) polarized vector beam has been obtained with a pulse duration of 440 fs (430 fs) and a maximum average output power of 20.36 W (20.12 W). The maximum output pulse energy is ∼20 μJ at a repetition rate of 1 MHz, corresponding to a high peak power of ∼46 MW. The comparison between simulated intensity profiles and measured experimental results suggests that the generated CVBs have a remarkable intensity distribution. The proposed configuration of our laser system provides a promising solution for high quality CVBs generation with the characteristics of high peak power, ultrashort pulse duration, and high mode purity.