An improved understanding of the underlying mechanisms that drive catalytic pathways as well as surface-activity relationships are fundamental in the areas of design and optimization of industrially relevant heterogeneous catalytic systems, which aim to reduce the environmental footprint of chemical manufacturing. The advent of powerful, state-of-the-art magnetic resonance techniques promise to offer insight into structural features of such systems with molecular precision. The goal of my project is to further understanding of surface interactions between model paramagnetic vanadium(IV) complexes and metal oxide supports (such as porous Al2O3 and SiO2) using electron paramagnetic resonance (EPR) spectroscopy. The nature of, and the interaction of the vanadium with, the support affects the activity and selectivity, however the origins of these effects are still largely unknown. It is our hope that EPR spectroscopy, continuous wave as well as pulsed, will shed light into such elusive mechanisms.