A series of Se-Se-linked polystyrenes have been synthesized and subjected to pulse sonication. Comprehensive investigations based on GPC measurements, derivatization experiments, and EPR spectroscopy verify the sonication-induced bond scission and metathesis of these polymeric diselenides. The metathesis kinetics and energy conversion efficiency by different stimuli including heating, light, and sonication are compared, which demonstrate that sonication can offer an alternative way to break the Se-Se bond and realize selective metathesis reactions between diselenide-linked polymers and small molecules. This fundamental study on sonochemistry of diselenide-centered polymers expands our knowledge of diselenide chemistry and mechanochemistry of dynamic covalent mechanophores, which may greatly advance the applications of diselenide-containing polymers.