Network science draws from a number of fields to examine complex systems using nodes to represent individuals and connections to represent relationships between individuals to form a network. This approach has been used in several areas of Psychology to illustrate the influence that the structure of a network has on processing in that system. In the present study the concept of keyplayers in a network (Borgatti, 2006) was examined in the domain of Psycholinguistics. Keyplayers are nodes in a network that, when removed, result in the network fracturing into several smaller components. A set of such nodes was found in a network of phonological word-forms as was another set of foil words, comparable to the “keywords” on a number of lexical and network characteristics. In three conventional psycholinguistic tasks keywords were responded to more quickly and accurately than the foils. A similar trend was observed in an analysis of the keywords and foils (and another set of foils) in the English Lexicon Project. These results open avenues for further exploration of keywords in various areas of language processing, and demonstrate the utility of the network science approach to psycholinguistics and psychology more generally.