Chlorinated paraffins (CP) are complex molecular mixtures occurring in a wide range of isomers and homologs of environmental hazards, whose analytical complexity demand advanced mass spectrometry (MS) methods for their characterization. The reported formation of chlorinated olefins (COs) and other transformation products during CP biotransformation and degradation can alter the MS analysis, increasing the high resolution required to distinguish CPs from their degradation products. An advanced setup hyphenating a plasma ionization source and an external high-performance data acquisition and processing system to the legacy hybrid LTQ Orbitrap XL mass spectrometer is reported. First, the study demonstrated the versatility of a liquid sampling atmospheric pressure glow discharge, as a soft ionization technique, for CP analysis. Second, enhanced resolution and sensitivity provided by the absorption mode Fourier transform spectral representation on this legacy mass spectrometer are shown. The developed Orbitrap-based platform allowed the detection of new isotopic clusters and CPs and COs to be distinguished at medium resolution (setting 30,000 at m/z 400, ~ 400 ms transients), and even chlorinated di-olefins (CdiOs) at higher resolution (setting 100,000 at m/z 400, ~ 1500 ms transients). Overall, such proof-of-principle instrumental improvements are promising for environmental and analytical research in the field of CP analysis.