Traditional free-space laser communication systems use beacon and signal lights for target detection and alignment. However, these approaches are inaccurate owing to signal dispersion errors. To overcome this difficulty, we propose a new method using transient radio frequency (RF) signals to achieve highly accurate target detection and alignment. To validate the feasibility of our proposed method, we built an experimental multi-target space-laser communication system based on a rotating double prism and applied it to achieve multi-target space-laser communication. The results demonstrate the efficiency of the proposed method to capture multi-target positions in the field of view using wireless RF signals and a rotating double prism. In addition, we show that the system is capable of rapid scanning and accurate pointing as well as establishing a one-way stable communication with multiple targets. When the target is 36 cm away, the pointing accuracy of the system motor is less than 0.8°, the pointing time is 1.2 s, and the average pointing lateral error is 0.666 mm.