We introduce a universal high resolution mass spectrometric method for the analysis of poly(ionic liquid)s (PILs), which belong to the most challenging polyelectrolytes from an analytical perspective, by fusing high resolution collision-induced dissociation (CID)-Orbitrap mass spectrometry (MS) with supercharging agents as well as quadrupole time-of-flight (QToF) MS. The study includes a wide array of hydrophilic halide-containing PILs, which were analyzed in negative mode. The influence of the core structures (based on imidazolium, triazolium, ammonium, phosphonium and pyridinium moieties), and variable styrene-, acrylate- and vinyl-type IL polymers on the ionization behavior is mapped in detail. Variable end group functionalities were introduced via functional chain transfer agents (CTA) in reversible addition-fragmentation chain transfer (RAFT) polymerization to study their behavior during the MS analysis. Furthermore, the demanding class of vinylimidazolium halide IL polymers was investigated. The current contribution thus introduces a new analytical technology platform for an entire polymer class.