Through vial impedance spectroscopy (TVIS) provides a new process analytical technology for monitoring a development scale lyophilization process, which exploits the changes in the bulk electrical properties that occur on freezing and subsequent drying of a drug solution. Unlike the majority of uses of impedance spectroscopy, for freeze-drying process development, the electrodes do not contact the product but are attached to the outside of the glass vial which is used to contain the product to provide a non-sample-invasive monitoring technology. Impedance spectra (in frequency range 10 Hz to 1 MHz) are generated throughout the drying cycle by a specially designed impedance spectrometer based on a 1 GΩ trans-impedance amplifier and then displayed in terms of complex capacitance. Typical capacitance spectra have one or two peaks in the imaginary capacitance (i.e., the dielectric loss) and the same number of steps in the real part capacitance (i.e., the dielectric permittivity). This chapter explores the underlying mechanisms that are responsible for these dielectric processes, i.e., the Maxwell-Wagner (space charge) polarization of the glass wall of the vial through the contents of the vial when in the liquid state, and the dielectric relaxation of ice when in the frozen state. In future work, it will be demonstrated how to measure product temperature and drying rates within single vials and multiple (clusters) of vials, from which other critical process parameters, such as heat transfer coefficient and dry layer resistance, may be determined.