The stereoselective synthesis of (E)-bromovinyloxazolidinones was developed by the three-component reaction of propargylic amines, carbon dioxide, and N-bromosuccinimide in the presence of a silver catalyst with a base. Among the bases, a guanidine derivative has a significant effect on this bromination reaction. This catalytic reaction could be applied to various propargylic amines to produce the corresponding bromovinyloxazolidinones in good yields.