The transmission spectra of methylparaben, ethylparaben, propylparaben, and butylparaben in the range of 0.2–2.5 THz are measured using terahertz time-domain spectroscopy (THz-TDS). Their refractive index and absorption spectra are obtained at room temperature in nitrogen atmosphere. The results show that the four kinds of Nipagin esters have obvious absorption peaks at 1.54 and 1.83 THz for methylparaben, 1.98 THz for ethylparaben, 1.37 and 1.61 THz for propylparaben, and 0.76 and 1.68 THz for butylparaben. Their anomalous dispersion of the refractive index appears at the corresponding position. Based on the density functional theory (DFT), the vibration absorption spectra of their single molecule are simulated. The numerical simulation and experimental results generally agree with each other. Then the reasons for their minor differences are analyzed. Overall, the spectral properties of Nipagin esters are found to have great significance for the detection of preservatives and for food safety.