Motion planning and control of connected and autonomous vehicles (CAVs) for improving traffic efficiency and safety in intersections still meets many challenges due to its dynamic and complex nature. In this article, an innovative collision-free and time-optimal multivehicle motion planning method for the CAVs at unsignalized intersection scenarios is proposed. We systematically analyze the regularity of intersection crossing mode and summarize the overall conflict scenario. To eliminate the vehicles potential collision, a learning-based iterative optimization (LBIO) algorithm is designed to solve the collision-free trajectories generating problem iteratively and offline. The terminal constraint set, terminal cost, and global safe constraints of the LBIO are constructed and updated from the historical data in previous iterations. The algorithm can finally converge to time-optimal trajectories for multivehicle only after several iterations. To apply the trained trajectories into the continuous intersection traffic flow, an online cluster-based motion planning (CBMP) algorithm is developed to coordinate the vehicle velocities and movements in the cooperative control area surrounding the intersection. With an LTV-MPC algorithm for the low-level control, the proposed approach is validated on the SUMO in typical intersection scenarios. The results show that the proposed method allows the potentially conflicting vehicles passing the intersection simultaneously and quickly without waiting, and significantly improves the overall traffic efficiency.