Vector Fitting (VF) is a recent macromodeling method that has been popularized by its use in many commercial software for extracting equivalent circuit's of simulated networks. Specifically for material measurement applications, VF is shown to estimate either the permittivity or permeability of a multi-Debye material accurately, even when measured in the presence of noise and interferences caused by test setup imperfections. A brief history and survey of methods utilizing VF for material measurement will be introduced in this work. It is shown how VF is useful for macromodeling dielectric materials after being measured with standard transmission line and free-space methods. The sources of error in both an admittance tunnel test device and stripline resonant cavity test device are identified and VF is employed for correcting these errors. Full-wave simulations are performed to model the test setup imperfections and the sources of interference they cause are further verified in actual hardware measurements. An accurate macromodel is attained as long as the signal-to-interference-ratio (SIR) in the measurement is sufficiently high such that the Debye relaxations are observable in the data. Finally, VF is applied for macromodeling the time history of the total fields scattering from a perfectly conducting wedge. This effort is an initial test to see if a time domain theory of diffraction exists, and if the diffraction coefficients may be exactly modeled with VF. This section concludes how VF is not only useful for applications in material measurement, but for the solution of modeling fields and interactions in general.