Phonological awareness, phonological memory, and phonological access to lexical storage play important roles in acquiring literacy. We examined the convergent, discriminant, and predictive validity of these phonological processing abilities (PPA) in 389 3-, 4-, and 5-year-old children. Confirmatory factor analysis supported the validity of each PPA as separate from general cognitive ability and separate from each other. Multigroup structural equation modeling (SEM) with mean structure demonstrated that older preschoolers have better developed latent PPA than younger preschoolers but that the structure of PPA is equivalent. RAN was found uniquely associated with letter knowledge and text discrimination in younger preschoolers, and PA was found uniquely associated with word reading skills in older preschoolers. Finally, general cognitive ability was only indirectly associated with emergent literacy via PPA. These results highlight the importance of PPA in the early literacy development of English-speaking preschool children.