Multi- and triblock copolymers based on 1,5-dioxepan-2-one/epsilon-caprolactone (DXO/CL) were investigated by MALDI-TOF MS to determine the influence of copolymer composition and architecture on the molecular structures at the individual chain level. The copolymer compositions, average block lengths, and molecular weights were determined by H-1 and C-13 NMR and by SEC, respectively. The structures of polyether-ester oligomers (linear, cyclic) as well as the chemical structures of their end groups were established on the basis of their MALDI-TOF mass spectra. The mass spectrum of PDXO homopolymer was relatively simple, however, complex mass spectra were obtained in the case of multi- and triblock copolymers and the mass spectra clearly discerned the molecular level effect of copolymer composition and copolymer type.