Underground contamination by non-aqueous phase liquids (NAPLs) becomes increasingly serious. Rapid and reliable detection of contaminated zone and degree is the first step to site remediation. In this paper, diesel and fine sand are used as experiment materials to investigate the applicability of using time-domain reflectometry (TDR) to detect LNAPLs contamination. The major work includes: measurement of dielectric constant and electrical conductivity for the diesel-water-air-sand mixtures; measurement of reflection waveform and dielectric constant for specimens with a diesel contaminated layer being sandwiched in sand. The experimental results show the followings: A significant decrease in both dielectric constant and electrical conductivity is observed for the diesel-water-air-sand mixtures when diesel displaces the pore water, and the content of diesel can be calculated by the model; insignificant change in dielectric properties is measured when diesel only displaces the pore gas; when the diesel contaminated sand is sandwiched between two saturated sand layers, the interfaces of the diesel contaminated layer can be identified by analyzing the reflection waveform; for field application, TDR method is valid for the case that LNAPLs seep into saturated sand layer, and the applicability of TDR method in vadose zone depends on the initial saturation of the sand layer. The findings obtained in this paper provide a guidance for the use of TDR for the field investigation of NAPLs contaminated site.