It has been suggested that attention is guided by two factors that operate during associative learning: a predictiveness principle, by which attention is allocated to the best predictors of outcomes, and an uncertainty principle, by which attention is allocated to learn about the less known features of the environment. Recent studies have shown that predictiveness-driven attention can operate rapidly and in an automatic way to exploit known relationships. The corresponding characteristics of uncertainty-driven attention, on the other hand, remain unexplored. In two experiments we examined whether both predictiveness and uncertainty modulate attentional processing in an adaptation of the dot probe task. This task provides a measure of automatic orientation to cues during associative learning. The stimulus onset asynchrony of the probe display was manipulated in order to explore temporal characteristics of predictiveness- and uncertainty-driven attentional effects. Results showed that the predictive status of cues determined selective attention, with faster attentional capture to predictive than to non-predictive cues. In contrast, the level of uncertainty slowed down responses to the probe regardless of the predictive status of the cues. Both predictiveness- and uncertainty-driven attentional effects were very rapid (at 250 ms from cue onset) and were automatically activated.