The low-kinetic energy collision-induced dissociation (CID) behavior of different sodiumcationized polylactide (PLA) oligomers was thoroughly investigated to shed some light on the analytical potentialities of CID experiments in the context of polymer characterization. Indeed, investigation of several end-groups modified PLA reveals that, in addition to the expected end-group specific dissociations, collisionally-excited PLA.Na ϩ suffer from a backbone cleavage. The so-obtained sodium-bound dimer cations consecutively undergo the loss of a monomeric residue that corresponds to neutral acrylic acid. The experimental observations, performed on a hybrid Q-ToF instrument, were totally corroborated by a theoretical study involving DFT calculations, molecular mechanics, and molecular dynamics calculations. . Such biodegradable polymers are often designed to degrade hydrolytically so that most of the widely studied biodegradable polymers belong to the polyester family and include polylactide (PLA), polyglycolide (PG), and associated copolymers [3]. PLA is certainly one of the most important synthetic biodegradable and biocompatible polymers attracting a huge interest for new and versatile synthetic procedures [4]. Polylactide and poly-(lactic acid) are, respectively, obtained by ring-opening polymerization (ROP) of lactide, the cyclic dimer of lactic acid, or by polycondensation of lactic acid.In the course of our research on the polymerization of lactide using non-organometallic catalysts such as N-heterocyclic carbenes, superbases, fluorinated tertiary alcohols, thiourea derivatives, and phosphazenes [5][6][7], we decided to explore the potential of mass spectrometry to provide an in-depth characterization of synthetic polymers in addition to well-established methodologies, such as gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR). Electrospray ionization (ESI) and matrix-assisted laser desorption ionization (MALDI) represent the most significant recent developments in ionization techniques for mass spectrometry analysis of synthetic polymers [8]. State-of-the-art mass spectrometry tools hold the promise of providing not only absolute molecular mass distributions [9] but also qualitative end-group and repeat-unit composition [10], as well as structural information such as branching and intramolecular ring formation [11]. By definition, MS experiments provide the masses of the individual oligomers prepared during the polymer synthesis. On the basis of the m/z ratio of the detected cationized oligomers, compositional pieces of information such as the number and type of monomer units but also the nature of the incorporated end-groups can be derived. Nowadays, tandem mass spectrometry (MSMS) is emerging as an essential analytical methodology when accurate structural characterization of polymers cannot be unambiguously derived from single-stage MS experiments [12]. Recent MSMS investigations were successfully used to characterize individual functional groups of new polymers, to make