RATIONALEPolysulfides [poly(1,2‐alkylene sulfides)] are oxidation‐responsive polymers that are finding application in drug release and biomaterials. The precise knowledge of their macromolecular characteristics is of the essence in view of their application to biological systems.METHODSMatrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS) with and without silver trifluoroacetate was used to characterize a series of polymers with increasing molecular weight in the range 1000–4000 g/mol and with low polydispersity (