The multilayer structure of an ultra-high molecular weight polyethylene (UHMWPE) composite material was investigated in the terahertz (THz) spectral range by means of time-domain spectroscopy (TDS) technique. Such structures consist of many alternating layers of fibers, each being perpendicular to the other and each having a thickness of about 50 μm. Refractive indices of two composite samples and of a sample composed of four single layers (plies) having the same fiber orientation were determined for two orthogonal orientations of the electric field in a transmission TDS system. The birefringence of a single layer was measured, and the origin of this phenomenon is discussed. Using the TDS system in reflection, the formation of many pulses shifted in time was observed originating from reflections from interfaces of successive layers caused by the periodic modulation of the refractive index along the propagation of the THz radiation. This phenomenon is theoretically described and simulated by means of a transfer matrix method (TMM). A time-domain fitting procedure was used to determine thicknesses of all layers of the composite material. The reconstructed waveform based on the optimized thicknesses shows very good agreement with the measured waveform, with typical differences between measurements and simulations between 3 and 7 μm (depending on the sample). As a result, we were able to determine the thicknesses of all layers of two multilayer (~200 plies) structures by means of the reflection TDS technology with high accuracy.