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In impulse radio-ultra wideband (IR-UWB) positioning system, clock frequency offset is an important factor affecting the accuracy of ranging and angular measurement. Aiming at the problem of low accuracy of frequency offset estimation under complex multipath, an IR-UWB adaptive frequency offset estimation algorithm adapted to complex multipath environment is designed. First, with the advantage of anti-multipath of pulsed ultra-wideband signals, using the real-time estimated channel impulse response as an adaptive matched filtering template. Correct extraction of correlation peaks under complex multipath is guaranteed. Then, the phase sequence of the leading symbols is obtained using the associated peak spoke angle information. Finally, Bayesian estimation algorithm is used to improve the accuracy of frequency offset estimation. Simulations were performed under CM1~CM2 multipath channels in IEEE 802.15.4a standard. The simulation results show that the accuracy of frequency offset estimation can be guaranteed within 0.2 ppm under low SNR. The experimental results in tunnel environment show that the standard deviation of frequency offset estimation is less than 0.06 ppm within the range of 50 m. Highly accurate estimation of frequency offset in complex multipath environments are realized. It has strong practicability in complex multi-path environment.