Although many studies have been performed to investigate the spectral induced polarization (SIP) response of nonaqueous phase liquid (NAPL)-contaminated soil samples, there are still many uncertainties in the interpretation of the data. A key issue is that altered pore space geometries due to the presence of a NAPL phase will change the measured IP spectra. However, without any information on the NAPL distribution in the pore space, assumptions are necessary for the SIP data interpretation. Therefore, experimental data of SIP signals directly associated with different NAPL distributions are needed. We used high-resolution X-ray tomography and 3D image processing to quantitatively assess NAPL distributions in samples of fine-grained sand containing different concentrations of tetrachloroethylene and link this to SIP measurements on the same samples. The total concentration of the sample constituents as well as the volumes of the individual NAPL blobs were calculated and used for the interpretation of the associated SIP responses. The X-ray tomography and image analysis showed that the real sample properties (porosity and NAPL distributions) differed from the targeted ones. Both contaminated samples contained less NAPL than expected from the manual sample preparation. The SIP results showed higher real conductivity and lower imaginary conductivity in the contaminated samples compared to a clean sample. This is interpreted as an effect of increased surface conductivity along interconnected NAPL blobs and decreased surface areas in the samples due to NAPL blobs larger than and enclosing grains. We conclude that the combination of SIP, X-ray tomography, and image analysis is a very promising approach to achieve a better understanding of the measured SIP responses of NAPL-contaminated samples.