Fluorinated organic contaminants, including per- and polyfluoroalkyl substances (PFASs) and fluorinated pesticides and pharmaceuticals (FPPs), pose a persistent threat to environmental health. Widely used liquid chromatography-tandem mass spectrometry (LC-MS/MS) methods fail to capture large fractions of total organofluorine in environmental samples, confounding the assessment of fluorinated contamination. Fluorine-19 nuclear magnetic resonance spectroscopy (¹⁹F-NMR) is an inclusive method for total and class-based organofluorine analysis. Here, we apply ¹⁹F-NMR to 31 effluent, surface water, and foam samples collected at 13 potential organofluorine point sources or source regions and compare the results to targeted LC-MS/MS for 34 or 64 PFASs. LC-MS/MS detected a median of 11.4% of total organofluorine detected by ¹⁹F-NMR (range: nondetect to 8190 nM F ¹⁹F-NMR; nondetect to 8010 nM F LC-MS/MS). The highest ¹⁹F-NMR total organofluorine concentrations, detected in wastewater treatment plant (WWTP)-associated foam and at a soy oil production facility, arose from resonances characteristic of per- and polyfluorinated alkyl chains. ¹⁹F-NMR resonances from aryl CF₃ moieties were abundant in the WWTP-associated samples, consistent with prior reports of substantial contributions from pharmaceuticals to WWTP effluents. ¹⁹F-NMR enables the quantitative assessment of total organofluorine and qualitative insight into fluorinated structures, providing complementary analysis of organofluorine compounds missed by targeted mass spectrometry-based protocols.