The refined characterization of groundwater pollution is an important prerequisite for efficient and effective remediation. A high-resolution survey of a contaminated site in a chemical pesticide factory was carried out using non-invasive geophysical sensing technology. Modern electrical resistivity tomography (ERT) technology can rapidly identify and characterize the groundwater pollution plumes of organochlorine pesticides, which was demonstrated in this study by the significantly abnormal resistivity sensing in stratums and aquifers under the raw material tanks, production, and loading areas. The results were found to be highly consistent with the ERT sensing results achieved via incorporating borehole sampling and hydrochemical analysis. With high abnormal resistivity, the range of contamination within the profile was characterized on the meter level. We also unexpectedly found new pollution and explained its source. This study confirmed that the modern refined ERT method has a high feasibility and accuracy in characterizing the spatial distribution of organochlorine pesticide plumes in groundwater.