To meet the requirements for high-risk testing scenarios in the safety assessment of advanced driver assistance systems (ADASs), this study selected 239 vehicle-to-powered two-wheeler accidents occurring in Xiangtan County from the China In-depth Mobility Safety Study—Traffic Accident (CIMSS-TA) database. Seven scenario elements were selected from the levels of static road elements, dynamic traffic participants and environment elements. The accident characteristics were obtained through statistical analysis. The results showed that 75.73% of accidents occurred at T-junctions/intersections, and 34.73% were caused by visual obstructions. Six typical vehicle-to-powered two-wheeler crash scenarios were established by cluster analysis, including two straight road scenarios (scenarios 3 and 6), two T-junction scenarios (scenarios 1 and 5) and two intersection scenarios (scenarios 2 and 4). Furthermore, six vehicle-to-powered two-wheeler testing scenarios, which represent the traffic environment characteristics of Chinese county-level districts, were constructed by analysing the vehicle/powered two-wheeler speed, the first collision point of the vehicle, the obstacle type and location, etc. The results showed that the vehicle speed in scenario 4 was higher than that in scenario 2, with average values of 34.32 km/h and 21.99 km/h, respectively. The results of this study provide testing scenarios for the safety assessment of ADASs, and contribute to improving vehicle active safety technology