It is well known that non-line-of-sight (NLOS)error has been the major factor impeding the enhancement ofaccuracy for time of arrival (TOA) estimation and wirelesspositioning. This article proposes a novel method of TOAestimation effectively reducing the NLOS error by 60%,comparing with the traditional timing and synchronizationmethod. By constructing the orthogonal training sequences,this method converts the traditional TOA estimation to thedetection of the first arrival path (FAP) in the NLOS multipathenvironment, and then estimates the TOA by the round-triptransmission (RTT) technology. Both theoretical analysis andnumerical simulations prove that the method proposed in thisarticle achieves better performance than the traditional methods.