For many decades, the capacity for mass spectrometry (MS) to analyse matter in all of its forms was shackled by an inability to ionise large molecules into the gas phase. It was only in the late 1980s, when the capabilities of the ‘soft’ ionisation protocols of matrix-assisted laser desorption/ionisation (MALDI) and electrospray ionisation (ESI) became apparent, that these shackles were effectively removed. The emergence of soft ionisation methodologies acted as a driving force for significant advances in MS instrumentation; as a result, MS now represents one of the most potent means by which insights into the structural details of synthetic polymer samples can be obtained. However, despite MS being acknowledged to be a mainstream analytical tool in the field of polymer chemistry, the number of MS-based studies into polymer systems remains significantly limited when compared to other analytical methods, and it would thus appear that MS is still being severely underutilised. In this Trend article, important fundamental concepts of soft ionisation MS are presented in a tutorial style fashion within the context of the analysis of polymer systems, and the remarkable breadth, power and versatility of these techniques is illustrated using selected examples. We suggest that MS-based analyses represent one of the most promising areas of research in polymer science, and that the polymer chemistry community would be well served by utilising this analytical discipline in a more intensive manner.