The focus of this study was to observe the location and form of a NAPL in a three-fluid-phase (air-NAPL-water) soil system utilizing an advanced microscopic technique, cryo-scanning electron microscopy (cryo-SEM) with X-ray analysis. A sandy aquifer material was brought to residual water (NaCl saturated) saturation (∼4% by pore volume) followed by NAPL (iodobenzene) saturation, ranging from ∼1% to 80%, using modified Tempe® pressure cells. A small intact soil core was obtained from the pressure cell and quickly frozen in liquid nitrogen. The core was fractured and chromium coated at a high vacuum and −130°C. Secondary electron images (SEI) and X-ray dot maps (Si, Cl and I) were made of samples with different NAPL saturations. Photomicrographs and X-ray dot maps confirmed the existence of continuous NAPL films on soil (containing a residual water saturation) at high NAPL saturations. Photomicrographs revealed v-shaped wedges, pendular rings and films on irregular shaped sand grains. At low NAPL saturations (∼1% by pore volume), iodine was virtually nondetectable in the overall X-ray analysis of the sample. This suggests that the small quantity of NAPL present in the sample probably existed as thin films or small isolated lenses or blobs.