Overtaking case is a common traffic situation, but it is likely to pose a threat to traffic safety. To ensure reliable communication, it is necessary to study the characteristics of wireless channel under overtaking cases. In this paper, we focus on Vehicle-to-Vehicle (V2V) radio channel characteristics based on measurements at 5.9GHz. Through research and analysis, we can present empirical results of propagation channels in four scenarios. Our main concern is the difference in channel characteristics between overtaking and non-overtaking case. We propose a method to divide overtaking cases and non-overtaking cases points based on small-scale fading distribution, and results show that the dividing point is about 11 meters between the measured vehicles. Judging by Akaike Information Criterion(AIC), Weibull distribution is best under overtaking cases, while it follows Ricean distribution under non-overtaking. Then, we prove that the result of the AIC decision is valid by the Kolmogorov-Smirnov test. Therefore, we further compare Weibull β-factor and Ricean K-factor under two cases. The values of root-mean-square (RMS) delay spreads and average fade duration under overtaking cases are higher than those under non-overtaking, but RMS Doppler spreads and the level crossing rate are smaller than those under non-overtaking. The cross-correlation between RMS delay spread and Ricean K-factor is also calculated. The correlation value in OT case is higher than that in NOT case. The value of the correlation in the case of overtaking is higher than the case of non-overtaking. By comparing the above methods, it is proved that the dividing point between overtaking cases and nonovertaking cases is effective. INDEX TERMS V2V communication, channel measurement, overtaking, channel estimation, channel modeling, cross-correlation.