Proactive cognition brain models are mainstream nowadays. Within these, preparation is understood as an endogenous, top-down function that takes place prior to the actual perception of a stimulus and improves subsequent behavior. Neuroimaging has shown the existence of such preparatory activity separately in different cognitive domains, however no research to date has sought to uncover their potential similarities and differences. Two of these, often confounded in the literature, are Selective Attention (information relevance) and Perceptual Expectation (information probability). We used EEG to characterize the mechanisms that pre-activate specific contents in Attention and Expectation. In different blocks, participants were cued to the relevance or to the probability of target categories, faces vs. names, in a gender discrimination task. Multivariate Pattern (MVPA) and Representational Similarity Analyses (RSA) during the preparation window showed that both manipulations led to a significant, ramping-up prediction of the relevant or expected target category. However, classifiers trained with data from one condition did not generalize to the other, indicating the existence of unique anticipatory neural patterns. In addition, a Canonical Template Tracking procedure showed that there was stronger anticipatory perceptual reinstatement for relevance than for expectation blocks. Overall, the results indicate that preparation during attention and expectation acts through distinguishable neural mechanisms. These findings have important implications for current models of brain functioning, as they are a first step towards characterizing and dissociating the neural mechanisms involved in top-down anticipatory processing.