This work investigates the current theories that have been used to explain the particle size effect on electrocatalytic activity. In particular, this work focuses on electronic structure effects, geometric shape effects, crystallographic orientation effects, support structure effects, and the concept of territory theory. To investigate these theories, gold and nickel-phosphorus nanowire arrays have been used as model systems for electrocatalytic testing of the hydrogen evolution reaction in basic medium. In this study, the current particle size effect theories cannot adequately account for the observed structure-sensitive trends that are exhibited in the aforementioned systems. This work systematically looks at each of these different theories and discusses new possible factors that could serve as a foundation for a new theory on structure-sensitive catalysis.