To understand the dielectric properties of PCC and better correlate them with type and severity of PCC internal defects, a study was conducted to evaluate PCC complex permittivity and magnetic permeability over a wideband of frequencies using both time domain and frequency domain techniques. Three measuring devices were designed and fabricated: a parallel plate capacitor, a coaxial transmission line, and transverse electromagnetic (TEM) horn antennae. The TEM horn antenna covers the microwave frequencies. The measurement technique involves a time domain setup that was verified by a frequency domain measurement. Portland cement concrete slabs, 60 by 75 by 14 cm, were cast; defects include delamination, delamination filled with water, segregation, and chloride contamination. In this paper, measurements using the TEM horn antennae and the feasibility of detecting flaws at microwave frequency are presented.