This article is written in honor of Bob Huggins for his many decades of contributions to solid state ionics and materials research. It also reviews oxide-based solid state ionic probes and tools developed by Bob Huggins and his coworkers to study and understand the properties of ionically transporting materials, and to affect and enhance catalytic behavior. Fundamental properties ranging from phase equilibria and diagrams, to stability regimes and thermodynamic functions, to oxygen transport, to sensing and catalysis can be investigated using these powerful tools. Several examples from author's previous work were provided to discuss their principles and to illustrate their utility and versatility.