Nonaqueous phase liquids (NAPLs) located at the surface of the water table and/or below the water table are often a significant source for groundwater contamination near current or former commercial/industrial facilities. Due to the complex and long history of many industrial sites, these NAPLs often contain a complex mixture of contaminants and as such can be difficult to fully characterize using conventional analytical methods. Remediation and risk assessment activities at sites containing NAPLs may, subsequently, be hindered as the contamination profile may not be fully understood. This paper demonstrates the application of bench‐scale 1H nuclear magnetic resonance (NMR) spectroscopy as a practical tool to assist with the characterization of complex NAPLs. Here, a NAPL collected from a contaminated site situated near a former chemical manufacturing facility was analyzed using a combination of one‐dimensional (1D) 1H NMR spectroscopy and two‐dimensional (2D) 1H J‐resolved spectroscopy (JRES). It is shown that 1D NMR experiments are useful in the rapid identification of the classes of compounds present, whereas 2D JRES NMR experiments are useful in identifying specific compounds. The use of benchtop NMR spectroscopy as a simple and cost effective tool to assist in the analysis of contaminated sites may help improve the practical characterization of many heavily contaminated sites and facilitate improved risk assessments and remedial strategies.