Nonintrusive measurements of plasma properties are essential to evaluate, and numerically simulate, the in-flight performance of electric propulsion systems. As a logical first step in the development of new diagnostic techniques, this work depicts the implementation of multiphoton ionization and coherent microwave scattering (MPI-CMS) in a gridded-ion accelerator operating on rare gases. Presented studies primarily comprise photoionization spectroscopy of ground & excited state-populations of both neutrals and ions – supplemented by optical emission spectroscopy and Langmuir probe derived plume properties. Results suggest the potential of MPI-CMS for non-intrusive measurements of specie number densities.